Construct Robust Epitaxial Growth of (101) Textured Zinc Metal Anode for Long Life and High Capacity in Mild Aqueous Zinc-Ion Batteries.

Aqueous zinc-metal batteries are considered to have the potential for energy storage due to their high safety and low cost. However, the practical applications of zinc batteries are limited by dendrite growth and side reactions. Epitaxial growth is considered an effective method for stabilizing Zn anode, especially for manipulating the (002) plane of deposited zinc. However, (002) texture zinc is difficult to achieve stable cycle at high capacity due to its large lattice distortion and uneven electric field distribution. Here, a novel zinc anode with highly (101) texture (denoted as (101)-Zn) is constructed. Due to unique directional guidance and strong bonding effect, (101)-Zn can achieve dense vertical electroepitaxy in near-neutral electrolytes. In addition, the low grain boundary area inhibits the occurrence of side reactions. The resultant (101)-Zn symmetric cells exhibit excellent stability over 5300 h (4 mA cm-2 for 2 mAh cm-2 ) and 330 h (15 mA cm-2 for 10 mAh cm-2 ). Meanwhile, the cycle life of Zn//MnO2 full cell is meaningfully improved over 1000 cycles.

Unlocking the Capacity of Bismuth Oxide by a Redox Mediator Strategy for High-Performance Aqueous Zn-Ion Batteries.

Many cathode materials store zinc ions based on the intercalation reaction mechanism in neutral aqueous Zn-ion batteries, and the structural design of the cathodes has been stuck in the curing mode by extending the ion diffusion channel. Here, we first develop halide ions to unlock the electrochemical activity of conversion-type Bi2O3 in aqueous Zn-ion batteries. Notably, the iodide ion shows the best performance compatibility with the Bi2O3 cathode. The electrochemical reaction mechanism studies show that iodide ions can be regarded as a redox medium to reduce the charge-transfer activation energy and motivate the conversion of Bi2O3 from Bi3+ to Bi0 during the cycle. Unsurprising, the discharge-specific capacity can reach 436.8 mAh g-1 at 0.5 A g-1 and achieve a cyclic lifespan of 6000 cycles at a current density of 3 A g-1. The activation of the Bi2O3 conversion reaction by iodide ions is of great significance for broadening the research range of ZIB cathode materials.

Dendrite inhibited and dead lithium activated dual-function additive for lithium metal batteries.

In this study, 2-fluoro-5-iodopyridine (2-F-5-IPy) was used as an electrolyte additive, which can not only protect the negative electrode effectively by forming a stable SEI, but also convert dead lithium into active lithium. Benefits from this are a capacity retention of a Li‖LiFePO4 cell after 300 cycles from 36.5% to 89.4%, and the symmetrical cell can work stably for more than 800 hours. Therefore, the addition of 2-F-5-IPy can effectively improve the performance of lithium metal batteries.

Multifunctional electrolyte additive for realizing high-temperature and high-voltage lithium metal batteries.

Methyl 1H-1,2,4-triazole-3-carboxylate (MTC) was added into lithium metal batteries as an electrolyte additive, and not only did this addition lead to formation of solid electrolyte interfaces to protect both the anode and cathode, but the added MTC also served as a Lewis base in removing HF from the electrolyte to prevent the electrolyte from deteriorating. Therefore, the addition of MTC, in an appropriate amount, can be very effective at improving the electrochemical performance of lithium metal batteries.

Isolated Fe-Co heteronuclear diatomic sites as efficient bifunctional catalysts for high-performance lithium-sulfur batteries.

The slow redox kinetics of polysulfides and the difficulties in decomposition of Li2S during the charge and discharge processes are two serious obstacles to the practical application of lithium-sulfur batteries. Herein, we construct the Fe-Co diatomic catalytic materials supported by hollow carbon spheres to achieve high-efficiency catalysis for the conversion of polysulfides and the decomposition of Li2S simultaneously. The Fe atom center is beneficial to accelerate the discharge reaction process, and the Co atom center is favorable for charging process. Theoretical calculations combined with experiments reveal that this excellent bifunctional catalytic activity originates from the diatomic synergy between Fe and Co atom. As a result, the assembled cells exhibit the high rate performance (the discharge specific capacity achieves 688 mAh g-1 at 5 C) and the excellent cycle stability (the capacity decay rate is 0.018% for 1000 cycles at 1 C).

A Dynamic and Self-Adapting Interface Coating for Stable Zn-Metal Anodes.

The zinc (Zn)-ion battery has attracted much attention due to its high safety and environmental protection. At present, the critical issues of the generation of dendrites and the accumulation of dead Zn on the surface will lead to a sharp decline of the battery life. Zn dendrites can be inhibited to some extent by constructing an interface protective coating. However, the existing rigid coating method cannot maintain conformal contact with Zn due to the volume change of Zn deposition and will cause fracture irreversibly during the cycle. Here, a highly self-adaptable poly(dimethylsiloxane) (PDMS)/TiO2- x coating is developed that can dynamically adapt to volume changes and inhibit dendrites growth. PDMS has high dynamic and self-adaptability due to the crosslinking of the B-O bond. In addition, the rapid and uniform transfer of Zn2+ is induced by the oxygen-vacancy-rich TiO2- x . The assembled cells still achieve 99.6% coulombic efficiency after 700 cycles at a current density of 10 mA cm-2 . The adaptive interface coating constructed provides a sufficient guarantee for the stable operation of the Zn anode.

High-Index Faceted Nanocrystals as Highly Efficient Bifunctional Electrocatalysts for High-Performance Lithium-Sulfur Batteries.

Precisely regulating of the surface structure of crystalline materials to improve their catalytic activity for lithium polysulfides is urgently needed for high-performance lithium-sulfur (Li-S) batteries. Herein, high-index faceted iron oxide (Fe2O3) nanocrystals anchored on reduced graphene oxide are developed as highly efficient bifunctional electrocatalysts, effectively improving the electrochemical performance of Li-S batteries. The theoretical and experimental results all indicate that high-index Fe2O3 crystal facets with abundant unsaturated coordinated Fe sites not only have strong adsorption capacity to anchor polysulfides but also have high catalytic activity to facilitate the redox transformation of polysulfides and reduce the decomposition energy barrier of Li2S. The Li-S batteries with these bifunctional electrocatalysts exhibit high initial capacity of 1521 mAh g-1 at 0.1 C and excellent cycling performance with a low capacity fading of 0.025% per cycle during 1600 cycles at 2 C. Even with a high sulfur loading of 9.41 mg cm-2, a remarkable areal capacity of 7.61 mAh cm-2 was maintained after 85 cycles. This work provides a new strategy to improve the catalytic activity of nanocrystals through the crystal facet engineering, deepening the comprehending of facet-dependent activity of catalysts in Li-S chemistry, affording a novel perspective for the design of advanced sulfur electrodes.

Basal-Plane-Activated Molybdenum Sulfide Nanosheets with Suitable Orbital Orientation as Efficient Electrocatalysts for Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are one of the most promising candidates for next-generation energy storage systems because of their high theoretical energy density. However, the shuttling behavior and sluggish conversion kinetics of lithium polysulfides (LiPSs) limit their practical application. Herein, B-doped MoS2 nanosheets are synthesized on carbon nanotubes (denoted as CNT@MoS2-B) to function as catalysts to boost the performance of Li-S batteries. The poor catalytic performance of the pristine MoS2 is revealed to be the result of unsuitable orbital orientation of the basal plane, which hinders the orbital overlap with sulfur species. B in CNT@MoS2-B is sp3 hybridized, and it has a vacant σ orbital perpendicular to the basal plane, which can maximize the head-on orbital overlap with S. The incorporation of B significantly increases the reactivity of MoS2 basal plane, which can facilitate the kinetics of Li2S formation and dissolution. With these merits, the S/CNT@MoS2-B cathodes deliver high rate capability and outstanding cycling stability, holding great promise for both scientific research and practical application. This work affords fresh insights for developing effective catalysts to accelerate LiPS conversion.

Efficient Polysulfide Trapping and Conversion on N-Doped CoTe2 via Enhanced Dual-Anchoring Effect.

Polysulfide shuttling and sluggish sulfur redox kinetics hinder the cyclability and rate capability of lithium-sulfur (Li-S) batteries. The intrinsic redox kinetics of sulfur cathodes strongly depends on the interaction between catalysts and sulfur species. Herein, N-doped CoTe2 is proposed as an effective dual-anchoring electrocatalyst, which can simultaneously bind Li and S atoms in lithium polysulfides via ionic Te-Li/N-Li bonding and coordinate covalent Co-S bonding. The incorporated N not only serves as enhanced lithiophilic site, but also an agent to improve the sulfiphilicity of the Co site as revealed by a series of experimental and computational results. Benefiting from these superiorities, the use of N-doped CoTe2 as a catalytic interlayer enables efficient operation of Li-S batteries in terms of impressive rate capability of 758 mAh g-1 at 4 C and very low capacity decay of 0.021% per cycle over 1000 cycles. The material and strategy demonstrated in this work may open the door toward developing more advanced Li-S electrocatalysts.

Precise Synthesis of Fe-N2 Sites with High Activity and Stability for Long-Life Lithium-Sulfur Batteries.

Precisely tuning the coordination environment of the metal center and further maximizing the activity of transition metal-nitrogen carbon (M-NC) catalysts for high-performance lithium-sulfur batteries are greatly desired. Herein, we construct an Fe-NC material with uniform and stable Fe-N2 coordination structure. The theoretical and experimental results indicate that the unsaturated Fe-N2 center can act as a multifunctional site for anchoring lithium polysulfides (LiPSs), accelerating the redox conversion of LiPSs and reducing the reaction energy barrier of Li2S decomposition. Consequently, the batteries based on a porous carbon nitride supported Fe-N2 site (Fe-N2/CN) host exhibit excellent cycling performance with a capacity decay of 0.011% per cycle at 2 C after 2000 cycles. This work deepens the understanding of the relationship between electronic structure of M-NC sites and the catalysis effect for the conversion of LiPSs. This strategy also provides a potent guidance for the further application of M-NC materials in advanced lithium-sulfur batteries.

Intercalation Pseudocapacitive Zn2+ Storage with Hydrated Vanadium Dioxide toward Ultrahigh Rate Performance.

The weak van der Waals interactions enable ion-intercalation-type hosts to be ideal pseudocapacitive materials for energy storage. Here, a methodology for the preparation of hydrated vanadium dioxide nanoribbon (HVO) with moderate transport pathways is proposed. Out of the ordinary, the intercalation pseudocapacitive reaction mechanism is discovered for HVO, which powers high-rate capacitive charge storage compared with the battery-type intercalation reaction. The main factor is that the defective crystalline structure provides suitable ambient spacing for rapidly accommodating and transporting cations. As a result, the HVO delivers a fast Zn2+ ion diffusion coefficient and a low Zn2+ diffusion barrier. The electrochemical results with intercalation pseudocapacitance demonstrate a high reversible capacity of 396 mAh g-1 at 0.05 A g-1 , and even maintain 88 mAh g-1 at a high current density of 50 A g-1 .

Building High Rate Capability and Ultrastable Dendrite-Free Organic Anode for Rechargeable Aqueous Zinc Batteries.

Aqueous zinc-ion batteries (ZIBs) are an alternative energy storage system for large-scale grid applications compared with lithium-ion batteries, when the low cost, safety, and durability are taken into consideration. However, the reliability of the battery systems always suffers from the serious challenge of the large Zn dendrite formation and "dead Zn," thus bringing out the inferior cycling stability, and even cell shorting. Herein, a dendrite-free organic anode, perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) polymerized on the surface of reduced graphene oxide (PTCDI/rGO) utilized in ZIBs is reported. Moreover, the theoretical calculations prove the reason for the low redox potential. Due to the protons and zinc ions coparticipant phase transfer mechanism and the high charge transfer capability, the PTCDI/rGO electrode provides superior rate capability (121 mA h g-1 at 5000 mA g-1, retaining the 95% capacity of that compared with 50 mA g-1) and a long cycling life span (96% capacity retention after 1500 cycles at 3000 mA g-1). In addition, the proton coparticipation energy storage mechanism of active materials is elucidated by various ex-situ methods.

Constructing the Efficient Ion Diffusion Pathway by Introducing Oxygen Defects in Mn2O3 for High-Performance Aqueous Zinc-Ion Batteries.

Mn-based cathodes are admittedly the most promising candidate to achieve the practical applications of aqueous zinc-ion batteries because of the high operating voltage and economic benefit. However, the design of Mn-based cathodes still remains challenging because of the vulnerable chemical architecture and strong electrostatic interaction that lead to the inferior reaction kinetics and rapid capacity decay. These intrinsic drawbacks need to be fundamentally addressed by rationally decorating the crystal structure. Herein, an oxygen-defective Mn-based cathode (Ocu-Mn2O3) is designed via a doping low-valence Cu-ion strategy. The oxygen defect can modify the internal electric field of the material and enhance the substantial electrostatic stability by compensating for the nonzero dipole moment. With the merits of oxygen deficiency, the Ocu-Mn2O3 electrode exhibits the significant diffusion coefficient in the range from 1 × 10-6 to 1 × 10-8, and good rate performance. In addition, the Ocu-Mn2O3 maintains the highly reversible cyclic stability with the capacity retention of 88% over 600 cycles. The charge storage mechanism is explored as well, illustrating that the oxygen defects can improve the electrochemical active sites of H+ insertion, achieving a better charge-storage capacity than Mn2O3.

Hierarchical Mn3 O4 Anchored on 3D Graphene Aerogels via C-O-Mn Linkage with Superior Electrochemical Performance for Flexible Asymmetric Supercapacitor.

Flexible asymmetric supercapacitors are more appealing in flexible electronics because of high power density, wide cell voltage, and higher energy density than symmetric supercapacitors in aqueous electrolyte. In virtues of excellent conductivity, rich porous structure and interconnected honeycomb structure, three dimensional graphene aerogels show great potential as electrode in asymmetric supercapacitors. However, graphene aerogels are rarely used in flexible asymmetric supercapacitors because of easily re-stacking of graphene sheets, resulting in low electrochemical activity. Herein, flower-like hierarchical Mn3 O4 and carbon nanohorns are incorporated into three dimensional graphene aerogels to restrain the stack of graphene sheets, and are applied as the positive and negative electrode for asymmetric supercapacitors devices, respectively. Besides, a strong chemical coupling between Mn3 O4 and graphene via the C-O-Mn linkage is constructed and can provide a good electron-transport pathway during cycles. Consequently, the asymmetric supercapacitor device shows high rate cycle stability (87.8 % after 5000 cycles) and achieves a high energy density of 17.4 µWh cm-2 with power density of 14.1 mW cm-2 (156.7 mW cm-3 ) at 1.4 V.

Redox Mediator: A New Strategy in Designing Cathode for Prompting Redox Process of Li-S Batteries.

The multistep redox reactions of lithium-sulfur batteries involve undesirably complex transformation between sulfur and Li2S, and it is tough to spontaneously fragmentate polysulfides into shorter chains Li2S originating from the sluggish redox kinetics of soluble polysulfide intermediates, causing serious polarization and consumption of sulfur. In this work, 3,4,9,10-perylenetetracarboxylic diimide (PTCDI)/G is employed as sulfur host to accelerate the conversion process between polysulfides and sulfur, which could facilitate the process of both charging and discharging. Moreover, PTCDI has strong adsorption capacity with polysulfides to restrain shuttle effect, resulting in promotional kinetics and cycle stability. A high initial capacity of 1496 mAh g-1 at 0.05 C and slight capacity decay of 0.009% per cycle at 5 C over 1500 cycles can be achieved. Moreover, the cathode could also achieve a high energy efficiency over 85% at 0.5 C. This research extends the knowledge into an original domain for designing high-performance host materials.

A Class of Catalysts of BiOX (X = Cl, Br, I) for Anchoring Polysulfides and Accelerating Redox Reaction in Lithium Sulfur Batteries.

The lithium-sulfur battery system contains a complex reaction process of sulfur involving multielectron reactions and phase conversions. Moreover, the diffusion of intermediate polysulfides during reduction and sluggish kinetic conversion of polysulfides into insoluble Li2S still plague the use of Li-S batteries. Herein, BiOX was employed as sulfur host material in Li-S batteries, which could integrate suppression of the shuttle effect and promote kinetics redox reactions of lithium polysulfides. The polar BiOX displays a robust chemical adsorption ability with polysulfides, and the electrocatalytic activity of BiOX would accelerate the fragmentation of polysulfides into shorter chains. The results indicate that the good polysulfide reactivity not only ensures the effective reduction of polarization but also performs high discharge capacity and stable cycle performance. The battery with a BiOCl/G-S cathode reveals a high capacity of 1414 mA h/g at a current of 0.1 C and a low capacity decay rate of 0.007% during 2000 cycles at a current of 2 C. This work proposes the prospect of application of the BiOX materials in lithium sulfur batteries.

Blocking Polysulfide with Co2B@CNT via "Synergetic Adsorptive Effect" toward Ultrahigh-Rate Capability and Robust Lithium-Sulfur Battery.

Li-S batteries have attracted great interest as the next-generation secondary batteries due to their high energy density, being environmentally friendly, and low price. However, the road to commercialization of lithium-sulfur batteries remains limited owing to the "shuttle effect" of soluble polysulfides, which results in the inferior cycle stability. Herein, a potent functional separator is developed to restrain the "shuttle effect" by coating Co2B@carbon nanotube layer on the commercialized polypropylene separator. In merits of the coadsorption of Co sites and B sites, such Co2B shows highly efficient polysulfides block (11.67 mg/m2 for Li2S6). Besides, the composite also exhibits obviously catalysis from Li2S8 to Li2S. By combining the fast electron transportation along the carbon nanotube, a superior rate performance is achieved with the modified separator and common carbon-sulfur cathode. Typically, the cell with Co2B@CNT shows prominent cycling life with a capacity degradation of 0.0072% per cycle (3000 cycles) and ultrahigh-rate capability at 5 C current (1172.8 mAh/g), which outstands the previously reported polysulfides barrier layer. The cell with Co2B@CNT can exhibit electrochemical performance at areal capacity of 5.5 mAh/cm2 (0.5 C) when the sulfur loading increased to 5.8 mg/cm2. This work defines an efficacious strategy to restrain the "shuttle effect" of polysulfides and shed light on the great potential of borides in Li-S battery.

MoP hollow nanospheres encapsulated in 3D reduced graphene oxide networks as high rate and ultralong cycle performance anodes for sodium-ion batteries.

Molybdenum phosphide (MoP), regarded as a promising anode material for sodium-ion batteries due to its superior conductivity and high theoretical specific capacity, still suffers from rapid capacity decay because of a large volume change and weak diffusion kinetics. Hollow nano-structures will be an effective solution to alleviate structural strain and improve cycling stability. Yet the preparation of MoP needs a high temperature phosphorization procedure which would cause agglomeration and structure collapse, making it difficult to achieve hollow nano-structures. Herein, caged by 3D graphene networks, MoP hollow nanospheres encapsulated in 3D reduced graphene oxide networks (H-MoP@rGO) were prepared successfully, and benefiting from the merits of the hollow nano-structure and flexibility of rGO, H-MoP@rGO demonstrates a superior cycle performance of 353.8 mA h g-1 at 1 A g-1 after 600 cycles and an extraordinary rate performance of 183.4 mA h g-1 at an ultrahigh current density of 10 A g-1 even after 3000 cycles.

SnS2 /SnO2 Heterostructures towards Enhanced Electrochemical Performance of Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have been recognized as outstanding candidates for energy storage systems due to their superiority in terms of energy density. To meet the requirements for practical use, it is necessary to develop an effective method to realize Li-S batteries with high sulfur utilization and cycle stability. Here, a strategy to construct heterostructure composites as cathodes for high performance Li-S batteries is presented. Taking the SnS2 /SnO2 couple as an example, SnS2 /SnO2 nanosheet heterostructures on carbon nanofibers (CNFs), named C@SnS2 /SnO2 , were designed and synthesized. Considering the electrochemical performance of SnS2 /SnO2 heterostructures, it is interesting to note that the existence of heterointerfaces could efficiently improve lithium ion diffusion rate so as to accelerate the redox reaction significantly, thus leading to the enhanced sulfur utilization and more excellent rate performance. Benefiting from the unique structure and heterointerfaces of C@SnS2 /SnO2 materials, the battery exhibited excellent cyclic stability and high sulfur utilization. This work may provide a powerful strategy for guiding the design of sulfur hosts from selecting the material composition to constructing of microstructure.

Ion-Selective Prussian-Blue-Modified Celgard Separator for High-Performance Lithium-Sulfur Battery.

Application of Li-S batteries has been restricted because of their major problem, that is, shuttling of soluble polysulfides between electrodes, which results in serious capacity fading. For the development of high-performance Li-S batteries, we first time utilize a simple growth method to introduce a Prussian blue (PB)-modified Celgard separator as an ion-selective membrane. The unique structure of PB could effectively suppress the shuttle of polysulfides but scarcely affect the transfer ability of lithium ions, which is beneficial to achieve high sulfur conversion efficiency and capacity retention. The Li-S battery with PB-modified Celgard separator has an average capacity decay of only 0.03 % per cycle at 1 C after 1000 cycles.