P-doped RuSe2 on Porous N-doped Carbon Matrix as Catalysts for Accelerated Sulfur Redox Reactions.

Monocomponent catalysts exhibit the limited catalytic conversion of polysulfides due to their intrinsic electronic structure, but their catalytic activity can be improved by introducing heteroatoms to regulate its electronic structure. However, the rational selection principles of doping elements remain unclear. Here, we are guided by theoretical calculations to select the suitable doping elements based on the balanced relationship between the adsorption strength of lithium polysulfides (LiPSs) and catalytic activity of lithium sulfide. We apply the screening method to develop a new catalyst of phosphorus doped RuSe2, manifesting the further enhanced conductivity compared with original RuSe2, facilitating charge transfer and further modulating the d-band center of RuSe2, thereby augmenting its effectiveness in interacting with LiPSs. Consequently, the assembled cell exhibits an areal capacity of 7.7 mAh cm-2, even under high sulfur loading of 8.0 mg cm-2 and a lean electrolyte condition (5.0 µL mg-1). This rational screening strategy offers a robust solution for the design of advanced catalysts in the field of lithium-sulfur batteries and potentially other domains as well.

Rational Design of Flexible, Self-Supporting, and Binder-Free Prussian White/KetjenBlack/MXene Composite Electrode for Sodium-Ion Batteries with Boosted Electrochemical Performance.

Due to their cost-effectiveness, abundant resources, and suitable working potential, sodium-ion batteries are anticipated to establish themselves as a leading technology in the realm of grid energy storage. However, sodium-ion batteries still encounter challenges, including issues related to low energy density and constrained cycling performance. In this study, a self-supported electrode composed of Prussian white/KetjenBlack/MXene (TK-PW) is proposed. In the TK-PW electrode, the MXene layer is coated with Prussian white nanoparticles and KetjenBlack with high conductivity, which is conducive to rapid Na+ dynamics and effectively alleviates the expansion of the electrode. Notably, the electrode preparation method is uncomplicated and economically efficient, enabling large-scale production. Electrochemical testing demonstrates that the TK-PW electrode retains 74.9% of capacity after 200 cycles, with a discharge capacity of 69.7 mAh·g-1 at 1000 mA·g-1. Furthermore, a full cell is constructed, employing a hard carbon anode and TK-PW cathode to validate the practical application potential of the TK-PW electrode.

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.

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.

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 V2O3 cathodes.

One-step growth of ultrathin CoSe2 nanobelts on N-doped MXene nanosheets for dendrite-inhibited and kinetic-accelerated lithium-sulfur chemistry.

The practical application of lithium-sulfur (Li-S) batteries is inhibited by the shuttle effect of lithium polysulfides (LiPSs) and slow polysulfide redox kinetics on the S cathode as well as the uncontrollable growth of dendrites on the Li metal anode. Therefore, both cathode and anode sides must be considered when modifying Li-S batteries. Herein, two-dimensional (2D) ultrathin CoSe2 nanobelts are in situ grown on 2D N-doped MXene nanosheets (CoSe2@N-MXene) via one-step solvothermal process for the first time. Owing to its unique 2D/2D structure, CoSe2@N-MXene can be processed to crumpled nanosheets by freeze-drying and flexible and freestanding films by vacuum filtration. These crumpled CoSe2@N-MXene nanosheets with abundant active sites and inner spaces can act as S hosts to accelerate polysulfide redox kinetics and suppress the shuttle effect of LiPSs owing to their strong adsorption ability and catalytic conversion effect with LiPSs. Meanwhile, the CoSe2@N-MXene film (CoSe2@NMF) can act as a current collector to promote uniform Li deposition because it contains lithiophilic CoSe2 and N sites. Under the systematic effect of CoSe2@N-MXene on S cathode and Li metal anode, the electrochemical and safety performance of Li-S batteries are improved. CoSe2@NMF also shows excellent storage performances in flexible energy storage devices.

Ordered Vacancies as Sodium Ion Micropumps in Cu-Deficient Copper Indium Diselenide to Enhance Sodium Storage.

Unordered vacancies engineered in host anode materials cannot well maintain the uniform Na+ adsorbed and possibly render the local structural stress intense, resulting in electrode peeling and battery failure. Here, the indium is first introduced into Cu2Se to achieve the formation of CuInSe2. Next, an ion extraction strategy is employed to fabricate Cu0.54In1.15Se2 enriched with ordered vacancies by spontaneous formation of defect pairs. Such ordered defects, compared with unordered ones, can serve as myriad sodium ion micropumps evenly distributing in crystalline host to homogenize the adsorbed Na+ and the generated volumetric stress during the electrochemistry. Furthermore, Cu0.54In1.15Se2 is indeed proved by the calculations to exhibit smaller volumetric variation than the counterpart with unordered vacancies. Thanks to the distinct ordered vacancy structure, the material exhibits a highly reversible capacity of 428 mAh g-1 at 1 C and a high-rate stability of 311.7 mAh g-1 at 10 C after 5000 cycles when employed as an anode material for Sodium-ion batteries (SIBs). This work presents the promotive effect of ordered vacancies on the electrochemistry of SIBs and demonstrates the superiority to unordered vacancies, which is expected to extend it to other metal-ion batteries, not limited to SIBs to achieve high capacity and cycling stability.

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.

MXene-Based Current Collectors for Advanced Rechargeable Batteries.

As an indispensable component of rechargeable batteries, the current collector plays a crucial role in supporting the electrode materials and collecting the accumulated electrical energy. However, some key issues, like uneven resources, high weight percentage, electrolytic corrosion, and high-voltage instability, cannot meet the growing need for rechargeable batteries. In recent years, MXene-based current collectors have achieved considerable achievements due to its unique structure, large surface area, and high conductivity. The related research has increased significantly. Nonetheless, a comprehensive review of this area is seldom. Herein the applications and progress of MXene in current collector are systematically summarized and discussed. Meanwhile, some challenges and future directions are presented.

Origin of Phase Engineering CoTe2 Alloy Toward Kinetics-Reinforced and Dendrite-Free Lithium-Sulfur Batteries.

Slow electrochemistry kinetics and dendrite growth are major obstacles for lithium-sulfur (Li-S) batteries. The investigations over the polymorph effect require more endeavors to further access the related catalyst design principles. Herein, the systematic evaluation of CoTe2 alloy with two polymorphs regarding sulfur reduction reaction (SRR) and lithium plating/stripping is reported. As disclosed by theoretical calculations and electrochemical measurements, the orthorhombic (o-) and hexagonal (h-) CoTe2 make a substantial difference. The reactivity origin of the CoTe2 polymorphs is explored. The higher position of d-band centers for the Co atoms on the o-CoTe2 leads to a higher displacement of the antibonding state; the lower antibonding state occupancy, the more effective the interaction with the sulfide moieties and lithium. Hence, o-CoTe2 annihilates h-CoTe2 and exhibits better catalysis and more uniform lithium deposition, consolidated by excellent performance of full cell made of o-CoTe2 . It keeps stable charging/discharging for 800 cycles at 0.5 C with only 0.055% capacity decay per cycle and even achieves an areal capacity of 6.5 mAh cm-2 at lean electrolyte and high sulfur loading of 6.4 mg cm-2 . This work establishes the mechanistic perspective about the catalysts in Li-S batteries and provides new insight into the unified solution.

In Situ Anchoring Ultrafine ZnS Nanodots on 2D MXene Nanosheets for Accelerating Polysulfide Redox and Regulating Li Plating.

Lithium-sulfur (Li-S) battery is a promising energy storage system due to its cost effectiveness and high energy density. However, formation of Li dendrites from Li metal anode and shuttle effect of lithium polysulfides (LiPSs) from S cathode impede its practical application. Herein, ultrafine ZnS nanodots are uniformly grown on 2D MXene nanosheets by a low-temperature (60 °C) hydrothermal method for the first time. Distinctively, the ZnS nanodot-decorated MXene nanosheets (ZnS/MXene) can be easily filtered to be a flexible and freestanding film in several minutes. The ZnS/MXene film can be used as a current collector for Li-metal anode to promote uniform Li deposition due to the superior lithiophilicity of ZnS nanodots. ZnS/MXene powders obtained by freeze drying can be used as separator decorator to address the shuttle effect of LiPSs due to their excellent adsorbability. Theoretical calculation proves that the existence of ZnS nanodots on MXene can obviously improve the adsorption ability of ZnS/MXene with Li+ and LiPSs. Li-S full cells with composite Li-metal anode and modified separator exhibit remarkable rate and cycling performance. Other transition metal sulfides (CdS, CuS, etc.) can be also grown on 2D MXene nanosheets by the low-temperature hydrothermal strategy.

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.

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.

Molybdenum Oxynitride Atomic Nanoclusters Bonded in Nanosheets of N-Doped Carbon Hierarchical Microspheres for Efficient Sodium Storage.

Transition metal nitrides have attracted considerable attention as great potential anode materials due to their excellent metallic conductivity and high theoretical specific capacity. However, their cycling performance is impeded by their instability caused by the reaction mechanism. Herein, we report the engineering and synthesis of a novel hybrid architecture composed of MoO2.0N0.5 atomic nanoclusters bonded in nanosheets of N-doped carbon hierarchical hollow microspheres (MoO2.0N0.5/NC) as an anode material for sodium-ion batteries. The facile self-templating strategy for the synthesis of MoO2.0N0.5/NC involves chemical polymerization and subsequent one-step calcination treatments. The design is beneficial to improve the electrochemical kinetics, buffer the volume variation of electrodes during cycling, and provide more interfacial active sites for sodium uptake. Due to these unique structural and compositional merits, these MoO2.0N0.5/NC exhibits excellent sodium storage performance in terms of superior rate capability and stable long cycle life. The work shows a feasible and effective way to design novel host candidates and solve the long-term cycling stability issues for sodium-ion batteries.

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.

Integrating Bi@C Nanospheres in Porous Hard Carbon Frameworks for Ultrafast Sodium Storage.

Sodium-ion batteries (SIBs) have emerged as an alternative technology because of their merits in abundance and cost. Realizing their real applications, however, remains a formidable challenge. One is that among the limitations of anode materials, the alloy-type candidates tolerate fast capacity fading during cycling. Here, a 3D framework superstructure assembled with carbon nanobelt arrays decorated with a metallic bismuth (Bi) nanospheres coated carbon layer by thermolysis of Bi-based metal-organic framework nanorods is synthesized as an anode material for SIBs. Due to the unique structural superiority, the anode design promotes excellent sodium-storage performance in terms of high capacity, excellent cycling stability, and ultrahigh rate capability up to 80 A g-1 with a capacity of 308.8 mAh g-1 . The unprecedented sodium-storage ability is not only attributed to the unique hybrid architecture, but also to the production of a homogeneous and thin solid electrolyte interface layer and the formation of uniform porous nanostructures during cycling in the ether-based electrolyte. Importantly, deeper understanding of the underlying cause of the performance improvement is illuminated, which is vital to provide the theoretical basis for application of SIBs.

Ultrastable and High-Rate 2D Siloxene Anode Enabled by Covalent Organic Framework Engineering for Advanced Lithium-Ion Batteries.

Siloxene as a new type of 2D material has wide potential applications due to its special structure. Especially, as anode for lithium-ion batteries, siloxene shows promising prospect due to its small volume change and low diffusion pathway. However, the unstable solid electrolyte interphase and low electronic conductivity lead to the low Coulombic efficiency, poor rate capability, and limited cycling performance. To settle the problems, a thin porous covalent organic framework (COF) coating layer is designed by in situ growth on micro-sized siloxene. With the inherent ionic conductive and electrolyte compatible advantages of COF, the engineered siloxene demonstrates superior electrochemical performance with 96% capacity retention at 8 A g-1 for 1500 cycles.

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.

Highly Reversible Zn Metal Anodes Enabled by Freestanding, Lightweight, and Zincophilic MXene/Nanoporous Oxide Heterostructure Engineered Separator for Flexible Zn-MnO2 Batteries.

Aqueous zinc (Zn)-ion batteries are regarded as promising candidates for large-scale energy storage systems because of their high safety, low cost, and environmental benignity. However, the dendrite issue of Zn anode hinders their practical application. Herein, a freestanding, lightweight, and zincophilic MXene/nanoporous oxide heterostructure engineered separator is designed to stabilize a Zn metal anode. The nanoporous oxides prepared by a one-step vacuum distillation technique afford the advantages of large surface area, high porosity, and homogeneous porous structure. The zincophilic MXene@oxides layer can homogenize the electric field distribution, facilitate ion diffusion kinetics, reduce local current density, and promote even Zn ionic flux, which will regulate uniform Zn deposition and suppress side reactions. Accordingly, dendrite-free Zn anodes with stable cyclability are achieved for over 500 h at an ultrahigh area capacity of 10 mAh cm-2. Besides, flexible, long-lifespan, and high-rate N/S-doped three-dimensional MXene@MnO2||Zn full cells are constructed with the engineered separator. Moreover, this strategy can be successfully extended to lithium, sodium, potassium, and magnesium metal batteries, indicating that separator regulation is a universal approach to overcome the challenges of metal batteries.

One-Step, Vacuum-Assisted Construction of Micrometer-Sized Nanoporous Silicon Confined by Uniform Two-Dimensional N-Doped Carbon toward Advanced Li Ion and MXene-Based Li Metal Batteries.

With the advantages of a high theoretical capacity, proper working voltage, and abundant reserves, silicon (Si) is regarded as a promising anode for lithium-ion batteries. However, huge volume expansion and low electronic conductivity impede the commercialization of Si anodes. We devised a one-step, vacuum-assisted reactive carbon coating technique to controllably produce micrometer-sized nanoporous silicon confined by homogeneous N-doped carbon nanosheet frameworks (NPSi@NCNFs), achieved by the solid state reaction of a commercial bulk precursor and the subsequent evaporation of byproducts. The graphitization degree, C and N contents of the carbon shell, as well as the porosity of Si can be regulated by adjusting the synthetic conditions. A rational structure can mitigate volume expansion to maintain structural integrity, enhance electronic conductivity to facilitate charge transport, and serve as a protected layer to stabilize the solid electrolyte interphase. The NPSi@NCNF anode enables a stable cycling performance with 95.68% capacity retention for 4000 cycles at 5 A g-1. Furthermore, a flexible 2D/3D architecture is designed by conjugating NPSi@NCNFs with MXene. Lithiophilic NPSi@NCNFs homogenize Li nucleation and growth, evidenced by structural evolutions of MXene@NPSi@NCNF deposited Li. The application potential of NPSi@NCNFs and MXene@NPSi@NCNFs is estimated via assembling full cells with LiNi0.8Co0.1Mn0.1O2 and LiNi0.5Mn1.5O4 cathodes. This work offers a method for the rational design of alloy-based materials for advanced energy storage.