Heterogenization-Activated Zinc Telluride via Rectifying Interfacial Contact to Afford Synergistic Confinement-Adsorption-Catalysis for High-Performance Lithium-Sulfur Batteries.

The notorious shuttle effect and sluggish conversion kinetics of intermediate polysulfides (Li2S4, Li2S6, Li2S8) are severely hindered the large-scale development of Lithium-sulfur (Li-S) batteries. Rectifying interface effect has been a solution to regulate the electron distribution of catalysts via interfacial charge exchange. Herein, a ZnTe-ZnO heterojunction encapsulated in nitrogen-doped hierarchical porous carbon (ZnTe-O@NC) derived from metal-organic framework is fabricated. Theoretical calculations and experiments prove that the built-in electric field constructed at ZnTe-ZnO heterojunction via the rectifying interface contact, thus promoting the charge transfer as well as enhancing adsorption and conversion kinetics toward polysulfides, thereby stimulating the catalytic activity of the ZnTe. Meanwhile, the nitrogen-doped hierarchical porous carbon acts as confinement substrate also enables fast electrons/ions transport, combining with ZnTe-ZnO heterojunction realize a synergistic confinement-adsorption-catalysis toward polysulfides. As a result, the Li-S batteries with S/ZnTe-O@NC electrodes exhibit an impressive rate capability (639.7 mAh g-1 at 3 C) and cycling performance (70% capacity retention at 1 C over 500 cycles). Even with a high sulfur loading, it still delivers a superior electrochemical performance. This work provides a novel perspective on designing highly catalytic materials to achieve synergistic confinement-adsorption-catalysis for high-performance Li-S batteries.

Self-Zincophilic Dual Protection Host of 3D ZnO/Zn⊂CF to Enhance Zn Anode Cyclability.

Zn dendrite growth and side reactions restrict the practical use of Zn anode. Herein, the design of a novel 3D hierarchical structure is demonstrated with self-zincophilic dual-protection constructed by ZnO and Zn nanoparticles immobilized on carbon fibers (ZnO/Zn⊂CF) as a versatile host on the Zn surface. The unique 3D frameworks with abundant zinc nucleation storage sites can alleviate the structural stress during the plating/stripping process and overpower Zn dendrite growth by moderating Zn2+ flux. Moreover, given the dual protection design, it can reduce the contact area between active zinc and electrolyte, inhibiting hydrogen evolution reactions. Importantly, density functional theory calculations and experimental results confirm that the introduced O atoms in ZnO/Zn⊂CF enhance the interaction between Zn2+ and the host and reduce Zn nucleation overpotential. As expected, the ZnO/Zn⊂CF-Zn electrode exhibits stable Zn plating/stripping with low polarization for 4200 h at 0.2 mA cm-2 and 0.2 mAh cm-2 . Furthermore, the symmetrical cell displays a significantly long cycling life of over 1800 h, even at 30 mA cm-2 . The fabricated full cells also show impressive cycling performance when coupled with V2 O3 cathodes.

Rapid Growth of Bi2Se3 Nanodots on MXene Nanosheets at Room Temperature for Promoting Sulfur Redox Kinetics.

Li-S batteries are hampered by problems with their cathodes and anodes simultaneously. The improvement of Li-S batteries needs to consider both the anode and cathode. Herein, a Bi2Se3@MXene composite is prepared for the first time by rapidly growing Bi2Se3 nanodots on two-dimensional (2D) MXene nanosheets at room temperature through simply adding high-reactive hydroxyethylthioselenide in Bi3+/MXene aqueous solution. Bi2Se3@MXene exhibits a 2D structure due to the template effect of 2D MXene. Bi2Se3@MXene can not only facilitate the conversion of lithium polysulfides (LiPSs) but also inhibit their shuttling in the S cathode due to its catalytic effect and adsorption force with LiPSs. Bi2Se3@MXene can also be used as an interfacial lithiophilic layer to inhibit Li dendrite growth in the Li metal anode. Theoretical calculations reveal that Bi2Se3 nanodots in Bi2Se3@MXene can effectively boost the adsorption ability with LiPSs, and the MXene in Bi2Se3@MXene can accelerate the electron transport. Under the bidirectional regulation of Bi2Se3@MXene in the Li metal anode and S cathode, the Li-S battery shows an enhanced electrochemical performance.

Fluorine- and Acid-Free Strategy toward Scalable Fabrication of Two-Dimensional MXenes for Sodium-Ion Batteries.

MXenes are emerging 2D materials that have gained great attention because of their unique physical-chemical properties. However, the wide application of MXenes is prohibited by their high cost and environmentally harmful synthesis process. Here a fluoride- and acid-free physical vacuum distillation strategy is proposed to directly synthesize a series of MXenes. Specifically, by introducing a low-boiling-point element into MAX and subsequently evaporating A elements via physical vacuum distillation, fluoride-free MXenes (Ti3C2Tx, Nb2CTx, Nb4C3Tx, Ta2CTx, Ti2NTx, Ti3CNTx, etc.) are fabricated. This is a green and one-step process without any acid/alkaline involved and with all reactions inside a vacuum tube furnace, avoiding any contamination to external environments. Besides, the synthetic temperature is controlled to regulate the layered structures and specific surface areas of MXenes. Accordingly, the synthesized Ti3C2Tx MXene exhibits improved sodium storage performance. This method may provide an alternative for the scalable production of MXenes and other 2D materials.

Synchronous Regulation of D-Band Centers in Zn Substrates and Weakening Pauli Repulsion of Zn Ions Using the Ascorbic Acid Additive for Reversible Zinc Anodes.

The advanced aqueous zinc-ion batteries (AZIBs) are still challenging due to the harmful reactions including hydrogen evolution and corrosion. Here, a natural small molecule acid vitamin C (Vc) as an aqueous electrolyte additive has been selectively identified. The small molecule Vc can adjust the d band center of Zn substrate which fixes the active H+ so that the hydrogen evolution reaction (HER) is restrained. Simultaneously, it could also fine-tune the solvation structure of Zn ions due to the enhanced electrostatics and reduced Pauli repulsion verified by energy decomposition analysis (EDA). Hence, the cell retains an ultra-long cycle performance of over 1300 cycles and a superior Coulombic efficiency (CE) of 99.5 %. The prepared full cells display increased rate capability, cycle lifetime, and self-discharge suppression. Our results shed light on the mechanistic principle of electrolyte additives on the performance improvement of ZIBs, which is anticipated to render a new round of studies.

Binary Sulfiphilic Nickel Boride on Boron-Doped Graphene with Beneficial Interfacial Charge for Accelerated Li-S Dynamics.

The "shuttle effect" and slow conversion kinetics of lithium polysulfides (LiPSs) are stumbling block for high-energy-density lithium-sulfur batteries (LSBs), which can be effectively evaded by advanced catalytic materials. Transition metal borides possess binary LiPSs interactions sites, aggrandizing the density of chemical anchoring sites. Herein, a novel core-shelled heterostructure consisting of nickel boride nanoparticles on boron-doped graphene (Ni3 B/BG), is synthesized through a graphene spontaneously couple derived spatially confined strategy. The integration of Li2 S precipitation/dissociation experiments and density functional theory computations demonstrate that the favorable interfacial charge state between Ni3 B and BG provides smooth electron/charge transport channel, which promotes the charge transfer between Li2 S4 -Ni3 B/BG and Li2 S-Ni3 B/BG systems. Benefitting from these, the facilitated solid-liquid conversion kinetics of LiPSs and reduced energy barrier of Li2 S decomposition are achieved. Consequently, the LSBs employed the Ni3 B/BG modified PP separator deliver conspicuously improved electrochemical performances with excellent cycling stability (decay of 0.07% per cycle for 600 cycles at 2 C) and remarkable rate capability of 650 mAh g-1 at 10 C. This study provides a facile strategy for transition metal borides and reveals the effect of heterostructure on catalytic and adsorption activity for LiPSs, offering a new viewpoint to apply boride in LSBs.

In Situ Electrochemically Activated Vanadium Oxide Cathode for Advanced Aqueous Zn-Ion Batteries.

The search for large-capacity and high-energy-density cathode materials for aqueous Zn-ion batteries is still challenging. Here, an in situ electrochemical activation strategy to boost the electrochemical activity of a carbon-confined vanadium trioxide (V2O3@C) microsphere cathode is demonstrated. Tunnel-structured V2O3 undergoes a complete phase transition to a layered, amorphous, and oxygen-deficient Zn0.4V2O5-m·nH2O on the first charge, thus allowing subsequent (de)intercalation of zinc cations on the basis of the latter structure, which can be regulated by the amount of H2O in the electrolyte. The electrode thus delivers excellent stability with a significantly high capacity of 602 mAh g-1 over 150 cycles upon being subjected to a low-current-rate cycling, as well as a high-energy density of 439.6 Wh kg-1 and extended life up to 10000 cycles with a 90.3% capacity retention. This strategy will be exceptionally desirable to achieve ultrafast Zn-ion storage with high capacity and energy density.

Sodiophilic Mg2+ -Decorated Ti3 C2 MXene for Dendrite-Free Sodium Metal Batteries with Carbonate-Based Electrolytes.

The advantages of sodium metal, such as abundant resources, low cost, high capacity, and high working potential, make it a promising metal anode. Unfortunately, the hazardous dendrite growth of sodium metal is one of the major hindrances for the practical application of sodium metal batteries (SMBs). By applying multifunctional Mg(II)@Ti3 C2 MXene as the protective layer for commercial Cu foil, the wettability of the electrolyte on the current collector is dramatically improved with the suppression of sodium dendrites. Moreover, the first-principles calculations prove that the surface of Mg(0001) is able to establish a connection with Na(111) growth, with Mg acting as the nucleation seed for sodium. The experimental results indicate that even when a high areal capacity of sodium (2 mAh cm-2 ) is deposited, no sodium dendrite is observed. Electrochemical tests, including symmetric cells, Na||Cu asymmetric cells, and full cells, prove the sodiophilic character of Mg2+ -decorated Ti3 C2 MXene. The results may also create a new pathway for developing other dendrite-free metal anodes, such as Li/K/Zn/Ca/Mg.

Scalable Synthesis of Nano-Sized Bi for Separator Modifying in 5V-Class Lithium Metal Batteries and Potassium Ion Batteries Anodes.

With the advantages of high theoretical-specific capacity and lowest working potential, lithium metal anode is considered as the most promising anode for next-generation batteries. Here, a scalable dealloying method is developed to prepare nano-sized bismuth (Bi). It is found that the Bi-modification can not only enhance the wettability of the commercial polyethylene separator but also suppresses the lithium dendrite growth. With the nano-sized Bi modified separator, 5V-class lithium metal batteries with commercial carbonate-based electrolyte show a 91% capacity retention ratio after 800 cycles. First-principle calculations prove that lithium atoms tend to deposit smoothly on the Bi surface. Moreover, for potassium ion batteries, nano-sized Bi shows a stable cycling performance and high capacity. The results may be useful for the development of high-energy and high-safety batteries.

Rationally Designed Three-Layered TiO2 @amorphous MoS3 @Carbon Hierarchical Microspheres for Efficient Potassium Storage.

Amorphous MoS3 has been an attractive electrode material for sodium-ion batteries and lithium-sulfur batteries. However, the potassium storage capability of amorphous MoS3 remains unreported. Herein, the construction of hybrid hierarchical microspheres composed of amorphous MoS3 nanosheets dual-confined with TiO2 core, and nitrogen-doped carbon shell layer (denoted as TiO2 @A-MoS3 @NC) via a self-templating method, combined with a low-temperature sulfurization process as a new anode material for potassium-ion batteries (PIBs), is reported. Benefitting from the unique structural merits including unique 1D chain structure, disordered arrangement of atoms and a large number of defects of amorphous MoS3 , more active heterointerfacial sites, effectively mitigated volume change, good electrical contact, and easy K+ ion migration, the TiO2 @A-MoS3 @NC microspheres exhibit excellent potassium-storage performance with high specific capacity, superior rate capability, and cycling stability.

Multifunctional Atomic Molybdenum on Graphene with Distinctive Coordination to Solve Li and S Electrochemistry.

The improvement of lithium-sulfur batteries is still impeded by notorious shuttling effect and sluggish kinetics on the S cathode, and rampant Li dendrite formation on the Li anode makes it worse. Herein, a type of single-atom dispersed Mo on nitrogen-doped graphene (Mo/NG) with a distinctive Mo-N2 O2 -C coordination structure first serving as a multifunctional material is designed by a structure-oriented strategy to solve Li and S electrochemistry. Mo/NG with superior intrinsic properties endowed by the unique coordination configuration adsorbs soluble polysulfides and promotes bidirectional conversion of LiPSs at the cathode side. Meanwhile, the suitable binding strength of Mo/NG with lithium ions endows it with an attractive lithiophilic feature. Specifically, Mo/NG is able to work as the adaptor to redistribute lithium ions on the interface of separator and homogenize the lithium ion flux. Due to the suitable binding ability with Li+ , it does not interfere with the diffusion of lithium ions across and provides tunnels exclusive to lithium ions to generate fast and homogeneous flux. Ascribed to such unique multifunctionality, Li-S batteries assembled with Mo/NG exhibit excellent electrochemical performance including long cycling stability over 1000 cycles and high areal capacities under high sulfur mass loading.

WSe2 Flakelets on N-Doped Graphene for Accelerating Polysulfide Redox and Regulating Li Plating.

The practical application of lithium-sulfur batteries is still limited by the lithium polysulfides (LiPSs) shuttling effect on the S cathode and uncontrollable Li-dendrite growth on the Li anode. Herein, elaborately designed WSe2 flakelets immobilized on N-doped graphene (WSe2 /NG) with abundant active sites are employed to be a dual-functional host for satisfying both the S cathode and Li anode synchronously. On the S cathode, the WSe2 /NG with a strong interaction towards LiPSs can act as a redox accelerator to promote the bidirectional conversion of LiPSs. On the Li anode, the WSe2 /NG with excellent lithiophilic features can regulate the uniform Li plating/stripping to mitigate the growth of Li dendrite. Taking advantage of these merits, the assembled Li-S full batteries exhibit remarkable rate performance and stable cycling stability even at a higher sulfur loading of 10.5 mg cm-2 with a negative to positive electrode capacity (N/P) ratio of 1.4 : 1.

Dual-Functional MgO Nanocrystals Satisfying Both Polysulfides and Li Regulation toward Advanced Lithium-Sulfur Full Batteries.

Lithium-sulfur battery (LSB) is regarded as a preferential option for next-generation energy-storage system, but the lithium polysulfides (LiPSs) shuttling effect and the uncontrollable growth of dendritic Li in the anode impede its commercial viability. To address both of the issues simultaneously, a well-designed hybrid of MgO ultrafine nanocrystals dispersed on graphene-supported carbon nanosheets (MCG) is developed via a facile self-template strategy as dual-functional host for both sulfur and lithium. Relying on the coordination of strong LiPS-capturing capability, the shuttling effect is inhibited. Furthermore, the lithiophilic configuration with high specific surface area induce homogenous Li deposition, thus preventing the formation of disordered lithium dendrite. Integrating all these advantages, a full cell based on S@MCG cathode and Li@MCG@Cu anode exhibits a stable capacity at 0.5 C for 150 cycles with a low capacity fading rate. Furthermore, the full cell achieves a high capacity retention of 85.5% at a high S areal loading of 3.82 mg cm-2 under the condition of a low electrolyte/sulfur ratio (E/S) of 6.5 µL mg-1 and negative/positive capacity ratio (N/P) of 3. This strategy satisfying both cathode and anode host provides a viable approach to realize high-energy-density and dendrite-free LSBs.

A High-Rate and Ultrastable Aqueous Zinc-Ion Battery with a Novel MgV2 O6 ·1.7H2 O Nanobelt Cathode.

High-safety and low-cost aqueous Zn-ion batteries have triggered an astounding investigation surge in the last 5 years and are becoming competitive alternatives for grid-scale energy storage. However, the implementation of this promising technology is still plagued by the lack of effective and affordable cathode materials that can enable high energy densities and an exceptional cycling stability. Herein, a novel vanadium-based oxide cathode based on MgV2 O6 ·1.7H2 O nanobelts, which delivers a high capacity (425.7 mAh g-1 at 0.2 A g-1 ), a robust rate capability (182.1 mAh g-1 at 10 A g-1 ), and an ultrastable cycle without any visible deterioration, as well as an adequate energy density (331.6 Wh kg-1 ), is developed. Such excellent electrochemical Zn-ion storage performance is believed to result from the fast ion-diffusion kinetics boosted by a stable layered structure and an ultrahigh intercalation pseudocapacitance reaction, which are also benefited by a typical H+ /Zn2+ co-insertion mechanism, accompanied by an atypical Zn2+ intercalation chemistry with a partial but irreversible Mg2+ -Zn2+ ion-exchange reaction during the initial discharge. These results provide key and enlightening insights into the design of high-performance vanadium oxide cathode materials.

Bimetal CoNi Active Sites on Mesoporous Carbon Nanosheets to Kinetically Boost Lithium-Sulfur Batteries.

In order to solve the problem that soluble polysulfide intermediates diffuse between cathode and anode during charging and discharging, which leads to rapid attenuation of battery cycle life, the separator modification materials come into people's sight. Herein, a mesoporous carbon-supported cobalt-nickel bimetal composite (CoNi@MPC) is synthesized and directly coated on the original separator to serve as a secondary collector for lithium-sulfur batteries. CoNi@MPC exhibits multiple Co-Ni active sites, able to catalyze the reactions of soluble polysulfides, specifically accelerating the generation and decomposition of insoluble Li2 S in lithiation and delithiation process testified by the electrochemical results and density functional theory calculation. Relying on the bifunctionality of CoNi@MPC composite, the shuttle effect of lithium polysulfides can be effectively alleviated. Moreover, porous carbon as the conductive scaffold favors the improvement of electronic conductivity. Benefiting from the above advantages, the cell with CoNi@MPC separator indicates significantly enhanced electrochemical performances with excellent cycling life over 500 cycles and superior rate capabilities.

Design of Robust, Lithiophilic, and Flexible Inorganic-Polymer Protective Layer by Separator Engineering Enables Dendrite-Free Lithium Metal Batteries with LiNi0.8 Mn0.1 Co0.1 O2 Cathode.

As a promising candidate for the high energy density cells, the practical application of lithium-metal batteries (LMBs) is still extremely hindered by the uncontrolled growth of lithium (Li) dendrites. Herein, a facile strategy is developed that enables dendrite-free Li deposition by coating highly-lithiophilic amorphous SiO microparticles combined with high-binding polyacrylate acid (SiO@PAA) on polyethylene separators. A lithiated SiO and PAA (lithiated-SiO/PAA) protective layer with synergistic flexible and robust features is formed on the Li metal anode via the in situ reaction to offer outstanding interfacial stability during long-term cycles. By suppressing the formation of dead Li and random Li deposition, reducing the side reaction, and buffering the volume changes during the lithium deposition and dissolution, such a protective layer realizes a dendrite-free morphology of Li metal anode. Furthermore, sufficient ionic conductivity, uniform lithium-ion flux, and interface adaptability is guaranteed by the lithiated-SiO and Li polyacrylate acid. As a result, Li metal anodes display significantly enhanced cycling stability and coulombic efficiency in Li||Li and Cu||Li cells. When the composite separator is applied in a full cell with a carbonate-based electrolyte and LiNi0.8 Mn0.1 Co0.1 O2 cathode, it exhibits three times longer lifespan than control cell at current density of 5 C.

Boosting Zinc-Ion Storage Capability by Effectively Suppressing Vanadium Dissolution Based on Robust Layered Barium Vanadate.

Vanadium-based compounds with an open framework structure have become the subject of much recent investigation into aqueous zinc-ion batteries (AZIBs) due to high specific capacity. However, there are some issues with vanadium dissolution from a cathode framework as well as the generation of byproducts during discharge that should not be ignored, which could cause severe capacity deterioration and inadequate cycle life. Herein, we report several barium vanadate nanobelt cathodes constructed of two sorts of architectures, i.e., Ba1.2V6O16·3H2O and BaV6O16·3H2O (V3O8-type) and BaxV2O5·nH2O (V2O5-type), which are controllably synthesized by tuning the amount of barium precursor. Benefiting from the robust architecture, layered BaxV3O8-type nanobelts (Ba1.2V6O16·3H2O) exhibit superior rate capability and long-term cyclability owing to fast zinc-ion kinetics, enabled by efficiently suppressing cathode dissolution as well as greatly eliminating the generation of byproduct Zn4SO4(OH)6·xH2O, which provides a reasonable strategy to engineer cathode materials with robust architectures to improve the electrochemical performance of AZIBs.

Atomic Tungsten on Graphene with Unique Coordination Enabling Kinetically Boosted Lithium-Sulfur Batteries.

Use of catalytic materials is regarded as the most desirable strategy to cope with sluggish kinetics of lithium polysulfides (LiPSs) transformation and severe shuttle effect in lithium-sulfur batteries (LSBs). Single-atom catalysts (SACs) with 100 % atom-utilization are advantagous in serving as anchoring and electrocatalytic centers for LiPSs. Herein, a novel kind of tungsten (W) SAC immobilized on nitrogen-doped graphene (W/NG) with a unique W-O2 N2 -C coordination configuration and a high W loading of 8.6 wt % is proposed by a self-template and self-reduction strategy. The local coordination environment of W atom endows the W/NG with elevated LiPSs adsorption ability and catalytic activity. LSBs equipped with W/NG modified separator manifest greatly improved electrochemical performances with high cycling stability over 1000 cycles and ultrahigh rate capability. It indicates high areal capacity of 6.24 mAh cm-2 with robust cycling life at a high sulfur mass loading of 8.3 mg cm-2 .

Electrochemical Insights, Developing Strategies, and Perspectives toward Advanced Potassium-Sulfur Batteries.

The boosting demand for high-capacity energy storage systems requires innovative battery technologies with low-cost and sustainability. The advancement of potassium-sulfur (K-S) batteries have been triggered recently due to abundant resource and cost effectiveness. However, the functional performance of K-S batteries is fundamentally restricted by the vague understanding of K-S electrochemistry and the imperfect cell components or architectures, facing the issues of low cathode conductivity, intermediate shuttle loss, poor anode stability, electrode volume fluctuation, etc. Inspired by considerable research efforts on rechargeable metal-sulfur batteries, the holistic K-S system can be stabilized and promoted through various strategies on rational physical regulation and chemical engineering. In this review, first an attempt is made to address the electrochemical kinetic concept of K-S system on the basis of the emerging studies. Then, the classification of performance-improving strategies is thoroughly discussed in terms of specific battery component and prospective outlooks in materials optimization, structure innovations, as well as relevant electrochemistry are provided. Finally, the critical perspectives and challenges are discussed to demonstrate the forward-looking developmental directions of K-S batteries. This review not only endeavors to provide a deep understanding of the electrochemistry mechanism and rational designs for high-energy K-S batteries, but also encourages more efforts in their large-scale practical realization.

Systematic Study of Alkali Cations Intercalated Titanium Dioxide Effect on Sodium and Lithium Storage.

The fast development of electrochemical energy storage devices necessitates rational design of the high-performance electrode materials and systematic and deep understanding of the intrinsic energy storage processes. Herein, the preintercalation general strategy of alkali ions (A = Li+ , Na+ , K+ ) into titanium dioxide (A-TO, LTO, NTO, KTO) is proposed to improve the structural stability of anode materials for sodium and lithium storage. The different optimization effects of preintercalated alkali ions on electrochemical properties are studied systematically. Impressively, the three electrode materials manifest totally different capacities and capacity retention. The efficiency of the energy storage process is affected not only by the distinctive structure but also by the suitable interlayer spacing of Ti-O, as well as by the interaction effect between the host Ti-O layer and alien cations with proper size, demonstrating the pivotal role of the sodium ions. The greatly enhanced electrochemical performance confirms the importance of rational engineering and synthesis of advanced electrode materials with the preintercalation of proper alkali cations.