Competitive Coordination of Sodium Ions for High-Voltage Sodium Metal Batteries with Fast Reaction Speed.

The unstable electrode-electrolyte interface and the narrow electrochemical window of normal electrolytes hinder the potential application of high-voltage sodium metal batteries. These problems are actually related to the solvation structure of the electrolyte, which is determined by the competition between cations coordinated with anions or solvent molecules. Herein, we design an electrolyte incorporating ethyl (2,2,2-trifluoroethyl) carbonate and fluoroethylene carbonate, which facilitates a pronounced level of cation-anion coordination within the solvation sheath by enthalpy changes to reduce the overall coordination of cation-solvents and increase sensitivity to salt concentration. Such an electrolyte regulated by competitive coordination leads to highly reversible sodium plating/stripping with extended cycle life and a high Coulombic efficiency of 98.0%, which is the highest reported so far in Na||Cu cells with ester-based electrolytes. Moreover, 4.5 V high-voltage Na||Na3V2(PO4)2F3 cells exhibit a high rate capability up to 20 C and an impressive cycling stability with an 87.1% capacity retention after 250 cycles with limited Na. The proposed strategy of solvation structure modification by regulating the competitive coordination of the cation provides a new direction to achieve stable sodium metal batteries with high energy density and can be further extended to other battery systems by controlling enthalpy changes of the solvation structure.

Heterostructured WOx/W2C Nanocatalyst for Li2S Oxidation in Lithium-Sulfur Batteries with High-Areal-Capacity.

Lithium-sulfur (Li-S) batteries show extraordinary promise as a next-generation battery technology due to their high theoretical energy density and the cost efficiency of sulfur. However, the sluggish reaction kinetics, uncontrolled growth of lithium sulfide (Li2S), and substantial Li2S oxidation barrier cause low sulfur utilization and limited cycle life. Moreover, these drawbacks get exacerbated at high current densities and high sulfur loadings. Here, a heterostructured WOx/W2C nanocatalyst synthesized via ultrafast Joule heating is reported, and the resulting heterointerfaces contribute to enhance electrocatalytic activity for Li2S oxidation, as well as controlled Li2S deposition. The densely distributed nanoparticles provide abundant binding sites for uniform deposition of Li2S. The continuous heterointerfaces favor efficient adsorption and promote charge transfer, thereby reducing the activation barrier for the delithiation of Li2S. These attributes enable Li-S cells to deliver high-rate performance and high areal capacity. This study provides insights into efficient catalyst design for Li2S oxidation under practical cell conditions.

Rational Design of Li-Wicking Hosts for Ultrafast Fabrication of Flexible and Stable Lithium Metal Anodes.

The ever-increasing development of flexible and wearable electronics has imposed unprecedented demand on flexible batteries of high energy density and excellent mechanical stability. Rechargeable lithium (Li) metal battery shows great advantages in terms of its high theoretical energy density. However, the use of Li metal anode for flexible batteries faces huge challenges in terms of its undesirable dendrite growth, poor mechanical flexibility, and slow fabrication speed. Here, a highly scalable Li-wicking strategy is reported that allows ultrafast fabrication of mechanically flexible and electrochemically stable Li metal anodes. Through the rational design of the interface and structure of the wicking host, the mean speed of Li-wicking reaches 10 m2 min-1 , which is 1000 to 100 000 fold faster than the reported electrochemical deposition or thermal infusion methods and meets the industrial fabrication speed. Importantly, the Li-wicking process results in a unique 3D Li metal structure, which not only offers remarkable flexibility but also suppresses the dendrite formation. Paring the Li metal anode with lithium-iron phosphate or sulfur cathode yields flexible full cells that possess a high charging rate (8.0 mA cm-2 ), high energy density (300-380 Wh kg-1 ), long cycling stability (over 550 cycles), and excellent mechanical robustness (500 bending cycles).

High-performance lithium-sulfur batteries enabled by regulating Li2S deposition.

Lithium-sulfur batteries (LSBs) have received intensive attention in recent years due to their high theoretical energy density derived from the lithiation of sulfur. In the discharge process, sulfur transforms into lithium polysulfides (LiPSs) that dissolve in liquid electrolytes and then into insoluble Li2S precipitated on the electrode surface. The electronically and ionically insulating Li2S leads to two critical issues, including the sluggish reaction kinetics from LiPSs to Li2S and the passivation of the electrode. In this regard, controlling the Li2S deposition is significant for improving the performance of LSBs. In this perspective, we have summarized the recent achievements in regulating the Li2S deposition to enhance the performance of LSBs, including the solution-mediated growth of Li2S, sulfur host enhanced nucleation and catalysis induced kinetic improvement. Moreover, the challenges and possibilities for future research studies are discussed, highlighting the significance of regulating the Li2S deposition to realize the high electrochemical performance and promote the practical uses of LSBs.

Hybrid Solid Polymer Electrolytes with Two-Dimensional Inorganic Nanofillers.

Solid polymer electrolytes are of rapidly increasing importance for the research and development of future safe batteries with high energy density. The diversified chemistry and structures of polymers allow the utilization of a wide range of soft structures for all-polymer solid-state electrolytes. With equal importance is the hybrid solid-state electrolytes consisting of both "soft" polymeric structure and "hard" inorganic nanofillers. The recent emergence of the re-discovery of many two-dimensional layered materials has stimulated the booming of advanced research in energy storage fields, such as batteries, supercapacitors, and fuel cells. Of special interest is the mass transport properties of these 2D nanostructures for water, gas, or ions. This review aims at the current progress and prospective development of hybrid polymer-inorganic solid electrolytes based on important 2D materials, including natural clay and synthetic lamellar structures. The ion conduction mechanism and the fabrication, property and device performance of these hybrid solid electrolytes will be discussed.

Metal/Oxide Interface Nanostructures Generated by Surface Segregation for Electrocatalysis.

Strong metal/oxide interactions have been acknowledged to play prominent roles in chemical catalysis in the gas phase, but remain as an unexplored area in electrocatalysis in the liquid phase. Utilization of metal/oxide interface structures could generate high performance electrocatalysts for clean energy storage and conversion. However, building highly dispersed nanoscale metal/oxide interfaces on conductive scaffolds remains a significant challenge. Here, we report a novel strategy to create metal/oxide interface nanostructures by growing mixed metal oxide nanoparticles on carbon nanotubes (CNTs) and then selectively promoting migration of one of the metal ions to the surface of the oxide nanoparticles and simultaneous reduction to metal. Employing this strategy, we have synthesized Ni/CeO2 nanointerfaces coupled with CNTs. The Ni/CeO2 interface promotes hydrogen evolution catalysis by facilitating water dissociation and modifying the hydrogen binding energy. The Ni/CeO2-CNT hybrid material exhibits superior activity for hydrogen evolution as a result of synergistic effects including strong metal/oxide interactions, inorganic/carbon coupling, and particle size control.

Stable alkali metal ion intercalation compounds as optimized metal oxide nanowire cathodes for lithium batteries.

Intercalation of ions in electrode materials has been explored to improve the rate capability in lithium batteries and supercapacitors, due to the enhanced diffusion of Li(+) or electrolyte cations. Here, we describe a synergistic effect between crystal structure and intercalated ion by experimental characterization and ab initio calculations, based on more than 20 nanomaterials: five typical cathode materials together with their alkali metal ion intercalation compounds A-M-O (A = Li, Na, K, Rb; M = V, Mo, Co, Mn, Fe-P). Our focus on nanowires is motivated by general enhancements afforded by nanoscale structures that better sustain lattice distortions associated with charge/discharge cycles. We show that preintercalation of alkali metal ions in V-O and Mo-O yields substantial improvement in the Li ion charge/discharge cycling and rate, compared to A-Co-O, A-Mn-O, and A-Fe-P-O. Diffraction and modeling studies reveal that preintercalation with K and Rb ions yields a more stable interlayer expansion, which prevents destructive collapse of layers and allow Li ions to diffuse more freely. This study demonstrates that appropriate alkali metal ion intercalation in admissible structure can overcome the limitation of cyclability as well as rate capability of cathode materials, besides, the preintercalation strategy provides an effective method to enlarge diffusion channel at the technical level, and more generally, it suggests that the optimized design of stable intercalation compounds could lead to substantial improvements for applications in energy storage.

Introduction to Supercapacitors.

Guest editors Zhaojun Han, Ruopian Fang, Dewei Chu, Da-Wei Wang and Kostya (Ken) Ostrikov, introduce this Nanoscale Advances themed issue on supercapacitors.

Rationalized design of hyperbranched trans-scale graphene arrays for enduring high-energy lithium metal batteries.

Lithium (Li) metal anode have shown exceptional potential for high-energy batteries. However, practical cell-level energy density of Li metal batteries is usually limited by the low areal capacity (<3 mAh cm-2) because of the accelerated degradation of high-areal capacity Li metal anodes upon cycling. Here, we report the design of hyperbranched vertical arrays of defective graphene for enduring deep Li cycling at practical levels of areal capacity (>6 mAh cm-2). Such atomic-to-macroscopic trans-scale design is rationalized by quantifying the degradation dynamics of Li metal anodes. High-energy Li metal cells are prototyped under realistic conditions with high cathode capacity (>4 mAh cm-2), low negative-to-positive electrode capacity ratio (1:1), and low electrolyte-to-capacity ratio (5 g Ah-1), which shed light on a promising move toward practical Li metal batteries.

Nanofluidic voidless electrode for electrochemical capacitance enhancement in gel electrolyte.

Porous electrodes with extraordinary capacitances in liquid electrolytes are oftentimes incompetent when gel electrolyte is applied because of the escalating ion diffusion limitations brought by the difficulties of infilling the pores of electrode with gels. As a result, porous electrodes usually exhibit lower capacitance in gel electrolytes than that in liquid electrolytes. Benefiting from the swift ion transport in intrinsic hydrated nanochannels, the electrochemical capacitance of the nanofluidic voidless electrode (5.56% porosity) is nearly equal in gel and liquid electrolytes with a difference of ~1.8%. In gel electrolyte, the areal capacitance reaches 8.94 F cm-2 with a gravimetric capacitance of 178.8 F g-1 and a volumetric capacitance of 321.8 F cm-3. The findings are valuable to solid-state electrochemical energy storage technologies that require high-efficiency charge transport.

Dynamic single-site polysulfide immobilization in long-range disorder Cu-MOFs.

The structural transformation of MOFs in a polysulfide electrode process is poorly understood. We report the electrochemical amorphization of Cu3(BTC)2 MOFs in polysulfide electrolyte. We unveil the dynamic single-site polysulfide immobilization at the interconvertible Cu2+/Cu+ cation centres upon polysulfide adsorption and desorption, along with the reversible distortion of the Cu-O square planar unit.

The Regulating Role of Carbon Nanotubes and Graphene in Lithium-Ion and Lithium-Sulfur Batteries.

The ever-increasing demands for batteries with high energy densities to power the portable electronics with increased power consumption and to advance vehicle electrification and grid energy storage have propelled lithium battery technology to a position of tremendous importance. Carbon nanotubes (CNTs) and graphene, known with many appealing properties, are investigated intensely for improving the performance of lithium-ion (Li-ion) and lithium-sulfur (Li-S) batteries. However, a general and objective understanding of their actual role in Li-ion and Li-S batteries is lacking. It is recognized that CNTs and graphene are not appropriate active lithium storage materials, but are more like a regulator: they do not electrochemically react with lithium ions and electrons, but serve to regulate the lithium storage behavior of a specific electroactive material and increase the range of applications of a lithium battery. First, metrics for the evaluation of lithium batteries are discussed, based on which the regulating role of CNTs and graphene in Li-ion and Li-S batteries is comprehensively considered from fundamental electrochemical reactions to electrode structure and integral cell design. Finally, perspectives on how CNTs and graphene can further contribute to the development of lithium batteries are presented.

More Reliable Lithium-Sulfur Batteries: Status, Solutions and Prospects.

Lithium-sulfur (Li-S) batteries have attracted tremendous interest because of their high theoretical energy density and cost effectiveness. The target of Li-S battery research is to produce batteries with a high useful energy density that at least outperforms state-of-the-art lithium-ion batteries. However, due to an intrinsic gap between fundamental research and practical applications, the outstanding electrochemical results obtained in most Li-S battery studies indeed correspond to low useful energy densities and are not really suitable for practical requirements. The Li-S battery is a complex device and its useful energy density is determined by a number of design parameters, most of which are often ignored, leading to the failure to meet commercial requirements. The purpose of this review is to discuss how to pave the way for reliable Li-S batteries. First, the current research status of Li-S batteries is briefly reviewed based on statistical information obtained from literature. This includes an analysis of how the various parameters influence the useful energy density and a summary of existing problems in the current Li-S battery research. Possible solutions and some concerns regarding the construction of reliable Li-S batteries are comprehensively discussed. Finally, insights are offered on the future directions and prospects in Li-S battery field.

Conductive porous vanadium nitride/graphene composite as chemical anchor of polysulfides for lithium-sulfur batteries.

Although the rechargeable lithium-sulfur battery is an advanced energy storage system, its practical implementation has been impeded by many issues, in particular the shuttle effect causing rapid capacity fade and low Coulombic efficiency. Herein, we report a conductive porous vanadium nitride nanoribbon/graphene composite accommodating the catholyte as the cathode of a lithium-sulfur battery. The vanadium nitride/graphene composite provides strong anchoring for polysulfides and fast polysulfide conversion. The anchoring effect of vanadium nitride is confirmed by experimental and theoretical results. Owing to the high conductivity of vanadium nitride, the composite cathode exhibits lower polarization and faster redox reaction kinetics than a reduced graphene oxide cathode, showing good rate and cycling performances. The initial capacity reaches 1,471 mAh g-1 and the capacity after 100 cycles is 1,252 mAh g-1 at 0.2 C, a loss of only 15%, offering a potential for use in high energy lithium-sulfur batteries.

A Sulfur-Rich Copolymer@CNT Hybrid Cathode with Dual-Confinement of Polysulfides for High-Performance Lithium-Sulfur Batteries.

A sulfur-rich copolymer@carbon nanotubes hybrid cathode is introduced for lithium-sulfur batteries produced by combining the physical and chemical confinement of polysulfides. The binderfree and metal-current-collector-free cathode of dual confinement enables an efficient pathway for the fabrication of high-performance sulfur copolymer carbon matrix electrodes for lithium-sulfur batteries.

3D Interconnected Electrode Materials with Ultrahigh Areal Sulfur Loading for Li-S Batteries.

Sulfur electrodes based on a 3D integrated hollow carbon fiber foam (HCFF) are synthesized with high sulfur loadings of 6.2-21.2 mg cm(-2) . Benefiting from the high electrolyte absorbability of the HCFF and the multiple conductive channels, the obtained electrode demonstrates excellent cycling stability and a high areal capacity of 23.32 mAh cm(-2) , showing great promise in commercially viable Li-S batteries.

Toward More Reliable Lithium-Sulfur Batteries: An All-Graphene Cathode Structure.

Lithium-sulfur (Li-S) batteries are attracting increasing interest due to their high theoretical specific energy density, low cost, and eco-friendliness. However, most reports of the high gravimetric specific capacity and long cyclic life are not practically reliable because of their low areal specific capacity derived from the low areal sulfur loading and low sulfur content. Here, we fabricated a highly porous graphene with high pore volume of 3.51 cm(3) g(-1) as the sulfur host, enabling a high sulfur content of 80 wt %, and based on this, we further proposed an all-graphene structure for the sulfur cathode with highly conductive graphene as the current collector and partially oxygenated graphene as a polysulfide-adsorption layer. This cathode structural design enables a 5 mg cm(-2) sulfur-loaded cathode showing both high initial gravimetric specific capacity (1500 mAh g(-1)) and areal specific capacity (7.5 mAh cm(-2)), together with excellent cycling stability for 400 cycles, indicating great promise for more reliable lithium-sulfur batteries.

Localized polyselenides in a graphene-coated polymer separator for high rate and ultralong life lithium-selenium batteries.

A graphene-coated polymer separator was developed for lithium-selenium batteries with pure selenium powder as the active material. The structure is a simple yet effective strategy for improving Li-Se battery's electrochemical performance, yielding long cycle life up to 1000 cycles with high capacity and excellent rate behavior.

A nitrogen-doped mesoporous carbon containing an embedded network of carbon nanotubes as a highly efficient catalyst for the oxygen reduction reaction.

A nitrogen-doped mesoporous carbon containing a network of carbon nanotubes (CNTs) was produced for use as a catalyst for the oxygen reduction reaction (ORR). SiO2 nanoparticles were decorated with clusters of Fe atoms to act as catalyst seeds for CNT growth, after which the material was impregnated with aniline. After polymerization of the aniline, the material was pyrolysed and the SiO2 was removed by acid treatment. The resulting carbon-based hybrid also contained some Fe from the CNT growth catalyst and was doped with N from the aniline. The Fe-N species act as active catalytic sites and the CNT network enables efficient electron transport in the material. Mesopores left by the removal of the SiO2 template provide short transport pathways and easy access to ions. As a result, the catalyst showed not only excellent ORR activity, with 59 mV more positive onset potential and 30 mV more positive half-wave potential than a Pt/C catalyst, but also much longer durability and stronger tolerance to methanol crossover than a Pt/C catalyst.

TiO2/graphene sandwich paper as an anisotropic electrode for high rate lithium ion batteries.

We designed an anisotropic electrode, in which Li(+) ion insertion and diffusion are anisotropic, by controlled growth of TiO2 nanosheets parallel to the surface of graphene paper. The anisotropic electrode gives a gravimetric capacity of 112 mA h g(-1) at an ultra-high rate of 100 C (corresponding to 36 s of charge-discharge), 3 times higher than that of a referenced isotropic electrode. The results indicate that such an anisotropic electrode can be useful in the search for high-power lithium ion batteries.