Germanium-Free Dense Lithium Superionic Conductor and Interface Re-Engineering for All-Solid-State Lithium Batteries against High-Voltage Cathode.

Li10GeP2S12 (LGPS) solid electrolyte is not affordable due to the high cost of Ge metal, making it economically unviable despite being a lithium superionic conductor. The synthesis of such solid electrolytes is much more time- and energy-consuming and needs an inert environment. Here, we report Si (silicon)-based composition [Li10SiP2S12 (LSiPS)] to make it cost-effective through microwave heating (MW). The total time for synthesis processes, including ball milling, heating rate, and heating dwell time, is ∼120 min, much less than the previous reports. We have also avoided vacuum sealing/Ar-purging to reduce the synthesis cost further. During MW heating, the densification process dominates over coarsening, resulting in a dense nanoflake morphology with a finer crystallite size. The synthesized LSiPS has a high fraction (∼89%) of more conducting tetragonal phase as identified by NMR analysis. Further, we modified the interface between the Li anode and LSiPS by forming a lithiophobic and lithiophilic kind of gradient interlayer to reduce the reduction of LSiPS and suppress the side reactions. The interface modification resulted in a better Li/LSiPS/Li cyclic performance for 1800 h at 0.2 mA/cm2 and 500 h at 1.0 mA/cm2. All-solid-state lithium-metal batteries (ASSLIB) have been developed against a high-voltage cathode (LCMO-coated LCO) and showed an excellent cycling performance with a reversible capacity of ∼110 mAh/g after 300 cycles.

Lower Diffusion-Induced Stress in Nano-Crystallites of P2-Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 Novel Cathode for High Energy Na-ion Batteries.

P2-type Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 (NMTNO) cathode is a preeminent electrode material for Na-ion batteries owing to its open prismatic framework, air-moisture stability, inexpensiveness, appealing capacity, environmental benignity, and Co-free composition. However, the poor cycling stability, sluggish Na-ion kinetics induced in bulk-sized cathode particles, cracking, and exfoliation in the crystallites remain a setback. To outmaneuver these, a designing strategy of a mechanically robust, hexagonal nano-crystallites of P2-type Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 (NMTNOnano ) electrode via quick, energy-efficient, and low-cost microwave-irradiated synthesis is proposed. For the first time, employing a unified experimental and theoretical approach with fracture mechanics analysis, the mechanism behind the enhanced performance, better structural stability, and lower diffusion-induced stress of NMTNOnano compared to micro-sized Na2/3 Ni1/3 Mn1/2 Ti1/6 O2 is unveiled and the electrochemical shock map is predicted. The NMTNOnano cathode provides 94.8% capacity retention after 100 cycles at 0.1 C with prolonged performance for 1000 cycles at 0.5 C. The practical viability of this cathode, tested in a full cell against a hard carbon anode delivered 85.48% capacity retention at 0.14 mA cm-2 after 200 cycles. This work bridges the gap in correlating the microstructural and electrochemical properties through experimental, theoretical (DFT), and fracture mechanics analysis, thereby tailoring efficient cathode with lower diffusion-induced stress for high-energy Na-ion batteries.

Regulating Polysulfide Conversion Kinetics Using Tungsten Diboride as Additive For High-Performance Li-S Battery.

The practical application of Li-S batteries is severely limited due to low sulfur utilization, sluggish sulfur redox kinetics, intermediate polysulfide dissolution/shuttling, and subsequent anode degradation. A smart cathode with efficient electrocatalyst and a protected anode is necessary. Herein, hollow carbon (HC) spheres are used as a sulfur host to improve the electrical conductivity and buffer the volume expansion of active materials. Considering the weak interaction between carbon and lithium polysulfides (LiPS), tungsten diboride (WB2 ) nanoparticles are used as a conductive additive. Both experimental and density functional theory (DFT) comprehensively exhibit that metallic WB2 nanoparticles can firmly anchor the LiPS through B-S bond formation, accelerate their electrocatalytic conversion, and immobilize them. DFT also reveals that boron interacts with LiPS either through molecular or dissociative adsorption depending on its boron layer arrangement in WB2 . Further, a freestanding lithiated-poly(4-styrene sulfonate) membrane constructed on lithium, offers a homogeneous Li-ion flux, stable interface, and protection from LiPS. Finally, cells with the HC-S+WB2  cathode and protected anode exhibit improved active material utilization, superior rate performance, and impressive cycling stability, even at high sulfur loading and less quantity of the electrolyte. Further, the pouch cells demonstrate high reversible capacity and an excellent capacity retention.

Artificial Organo-Fluoro-Rich Anode Electrolyte Interface and Partially Sodiated Hard Carbon Anode for Improved Cycle Life and Practical Sodium-Ion Batteries.

In this work, a strategy is introduced wherein without keeping any excess cathode, a practical full-cell sodium-ion battery has been demonstrated by utilizing a hard carbon (HC) anode and sodium vanadium fluorophosphate and carbon nanotube composite (NVPF@C@CNT) cathode. A thin, robust, and durable solid electrolyte interface (SEI) is created on the surface of HC through its incubation wetted with a fluoroethylene carbonate (FEC)-rich warm electrolyte in direct contact with Na metal. During the incubation, the HC anode is partially sodiated and passivated with a thin SEI layer. The sodium-ion full cell fabricated while maintaining N/P ∼1.1 showed the first cycle Coulombic efficiency of ∼97% and delivered a stable areal capacity of 1.4 mAh cm-2 at a current rate of 0.1 mA cm-2 realized for the first time to the best of our knowledge. The full cell also showed a good rate capability, retaining 1.18 mAh cm-2 of its initial capacity even at a high current rate of 0.5 mA cm-2, and excellent cycling stability, giving a capacity of ∼1.0 mAh cm-2 after 500 cycles. The current strategy presents a practical way to make a sodium-ion full cell, utilizing no excess cathode material, significantly saving cost and time.

Water-in-Salt Electrolyte-Based Extended Voltage Range, Safe, and Long-Cycle-Life Aqueous Calcium-Ion Cells.

The narrow electrochemical stability window (1.23 V) of an aqueous electrolyte hinders the practical realization of calcium-ion chemistries of high-energy-density and long-cycle-life batteries. Furthermore, developing an aqueous electrolyte that is low cost, is environmentally friendly, and has a wide voltage window is essential to designing safe, high-energy-density, and sustainable calcium-ion batteries. A calcium-based water-in-salt (WISE) aqueous electrolyte surpasses the narrow stability window by offering a 2.12 V wide window by suppressing the hydrogen evolution at the anode and minimizing the overall water activity at the cathode. A comprehensive theoretical study predicts the preferential reduction of salt aggregates over water to form a passivation layer at the electrode-electrolyte interface and enhance the electrolyte stability window. Additionally, Raman spectroscopy reveals that the calcium ion coordination number, which is the number of nitrate ions surrounding the calcium ions in the aqueous electrolyte, gradually increases with an increase in the electrolyte concentration, leading to a gradual decrease in the hydration number of the calcium ions. A full cell in WISE was demonstrated to exhibit an excellent rate capability and cycling stability with negligible capacity loss (0.01 per cycle), maintaining 80% capacity retention over 1800 cycles with ∼99.99% Coulombic efficiency. The full cell provides an energy density of 232 Wh kg-1 at a power density of 69 W kg-1 and a current rate of 0.15 A g-1. Even at a higher current rate of 5 A g-1, the battery delivers an energy density of 182 Wh kg-1 (based on the active mass of the anode). This is one of the best performances to date of all previously reported full-cell aqueous calcium-ion batteries. A fundamental understanding of the storage mechanism and a electrode degradation study was achieved. This work suggests and expands new avenues for the practical realization of low-cost, safe, eco-friendly, and high-performance aqueous calcium-ion batteries for future large storage applications.

Direct-Contact Prelithiation of Si-C Anode Study as a Function of Time, Pressure, Temperature, and the Cell Ideal Time.

Direct-contact prelithiation (PL) is a facile, practical, and scalable method to overcome the first-cycle loss and large volume expansion issues for silicon anode (with 30 wt % Si loading) material, and a detailed study is absent. Here, an understanding of direct-contact PL as a function of the PL time, and the effects of externally applied pressure (weight), microstructure, and operating temperature have been studied. The impact of PL on the Si-C electrode surfaces has been analyzed by electrochemical techniques and different microstructural analyses. The solid electrolyte interface (SEI) layer thickness increases with the increase in PL time and decreases after 2 min of PL time. The ideal PL time was found to be between 15 (PL-15) and 30 (PL-30) min with 83.5 and 97.3% initial Coulombic efficiency (ICE), respectively, for 20 g of externally applied weight. The PL-15 and PL-30 cells showed better cyclic stability than PL-0 (without prelithiation), with more than 90% capacity retention after 500 cycles at 1 A g-1 current density. The discharge capacities for PL-15 and PL-30 have been observed as highest at 45 °C operating temperature with limited cyclability. We propose here a synchronization strategy in prelithiation time, pressure, and temperature to achieve excellent cell performance.

Electrocatalytic Activity of Polyaniline in Magnesium-Sulfur Batteries.

Rechargeable magnesium-sulfur (Mg-S) batteries offer the potential for inexpensive energy storage alternatives to other metal-ion batteries for the grid scale and household applications. Despite all economic and resource advantages, Mg-S battery chemistry suffers from a complicated reaction mechanism and extremely slow reaction kinetics. To improve the kinetics, we improvise a new electrode architecture where a conductive polymer is used along with a carbon network. This report will bring an important insight of electrocatalytic activity of polyaniline, on the basis of free-radical coupling and is a completely new concept in Mg-S battery chemistry. By the combined electron spin resonance spectroscopy, X-ray photoelectron spectroscopy, and fluorescence lifetime measurements, we perceived that the polyaniline anchors the S3•- species from the electrolyte/catholyte through a free-radical-coupling process and thus promotes the reduction to end-discharged products, via a chemical adduct. The concept of free-radical catalysis in Mg/S batteries will open a new knowledge to enhance the active material utilization in the Mg-S batteries.

High Performance Lithium-Ion Batteries Using Layered 2H-MoTe2 as Anode.

The major challenges faced by candidate electrode materials in lithium-ion batteries (LIBs) include their low electronic and ionic conductivities. 2D van der Waals materials with good electronic conductivity and weak interlayer interaction have been intensively studied in the electrochemical processes involving ion migrations. In particular, molybdenum ditelluride (MoTe2 ) has emerged as a new material for energy storage applications. Though 2H-MoTe2 with hexagonal semiconducting phase is expected to facilitate more efficient ion insertion/deinsertion than the monoclinic semi-metallic phase, its application as an anode in LIB has been elusive. Here, 2H-MoTe2 , prepared by a solid-state synthesis route, has been employed as an efficient anode with remarkable Li+ storage capacity. The as-prepared 2H-MoTe2 electrodes exhibit an initial specific capacity of 432 mAh g-1 and retain a high reversible specific capacity of 291 mAh g-1 after 260 cycles at 1.0 A g-1 . Further, a full-cell prototype is demonstrated by using 2H-MoTe2 anode with lithium cobalt oxide cathode, showing a high energy density of 454 Wh kg-1 (based on the MoTe2 mass) and capacity retention of 80% over 100 cycles. Synchrotron-based in situ X-ray absorption near-edge structures have revealed the unique lithium reaction pathway and storage mechanism, which is supported by density functional theory based calculations.

Practical Aqueous Calcium-Ion Battery Full-Cells for Future Stationary Storage.

There is a pressing need for high-rate cycling and cost-effective stationary energy storage systems in concomitance with the fast development of solar, wind, and other types of renewable sources of energy. Aqueous rechargeable Ca-ion batteries have the potential to meet the growing demands of stationary energy storage devices because they are abundant and safe; they can also be manufactured at a low-cost and have a higher volumetric capacity. In this study, we have demonstrated a low-cost, safe, aqueous Ca-ion battery that is based on a low potential, lower specific weight, in situ polymerized polyaniline as an anode, and a high redox-potential open-framework structured potassium copper hexacyanoferrate as a cathode. The charge-discharge mechanism of this battery includes doping/dedoping of NO3- at the anode, and intercalation and deintercalation of Ca-ion at the cathode. This Ca-ion battery works successfully in a 2.5 M Ca(NO3)2 aqueous electrolyte that exhibits 70 Wh kg-1 specific energy at 250 W kg-1 and even maintains a high energy density of 53 Wh kg-1 at a higher rate of 950 W kg-1; this indicates a good rate capability (calculation based on anode active mass). At 0.8 A g-1, the battery provides an average specific capacity of 130 mA h g-1, exhibiting high Coulombic efficiency (∼96%), with 95% capacity retention of over 200 cycles across its life span, which is a new achievement in the electrochemical performance of aqueous Ca-ion batteries. Furthermore, the calcium-ion storage mechanism is investigated using high-end X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. Thus, this significant electrochemical performance of the anode and the cathode renders the battery a promising candidate in grid-scale storage applications.

Three-Dimensionally Reinforced Freestanding Cathode for High-Energy Room-Temperature Sodium-Sulfur Batteries.

Room-temperature sodium-sulfur (RT Na-S) battery cathodes suffer from poor conductivity, rapid dissolution of intermediate products, and potentially destructive volume change during cycling. The optimal way to minimize these problems could be a construction of a nanocomposite cathode scaffold combining different components selected for their particular functions. Here, we have combined the excellent electronic conductivity of reduced graphene oxide, polysulfide adsorption ability of the ultrafine manganese oxide nanocrystals, rapid ion/electron dissemination efficiency of nanosized sulfur, and outstanding mechanical stiffness and good electrical conductivity of Na alginate/polyaniline hybrid binder in a single electrode heterostructure. At 0.2 A g-1, an RT Na-S battery containing the freestanding cathode delivers an initial specific cap acity of 631 mA h g-1. By delivering a nominal discharge voltage of 1.81 V, our Na-S batteries bestow a high specific energy of 737 W h kg-1 at the 2nd cycle and 660 W h kg-1 was retained after 50 cycles. The effect of the amount of electrolyte additive is also well demonstrated in this study. The electrode fabrication process provides a new approach to tailor the design and preparation of effective cathodes for the room-temperature sodium-sulfur batteries.

Insights of Diffusion Doping in Formation of Dual-Layered Material and Doped Heterostructure SnS-Sn:Sb2S3 for Sodium Ion Storage.

Insights into the formation mechanism of a dual-layered and doped heterostructure material SnIIS-SnIV:Sb2S3 are reported. In the presence of mixed alkyl thiols, first nanotubes of Sb2S3 were formed, and upon introduction of Sn(IV), SnIIS was deposited onto the surface of these tubular structures. Upon further annealing at a constant temperature, sluggish transformation resulted in a Sn(II)S-Sn(IV) doped Sb2S3 heterostructure, which finally turned to flake-like layered doped Sb2S3 nanostructures. SnS and Sb2S3, both being layered materials, were explored for the study of Na-ion storage, and these heterostructures were observed to be superior in comparison to the individual materials as well as the final doped nanostructures. The mechanism of formation of the heterostructures, the epitaxy at the junction, the diffusion doping, and the dopant-induced axial exfoliations leading to the final doped structures were studied. The electrochemical conversions in the presence of Na ions were also investigated, and insights into the mechanisms of both are reported in this Letter.

Ionic liquid electrolytes supporting high energy density in sodium-ion batteries based on sodium vanadium phosphate composites.

Sodium-ion batteries (SIBs) are widely considered as alternative, sustainable, and cost-effective energy storage devices for large-scale energy storage applications. In this work, an easily fabricated sodium vanadium phosphate-carbon composite (NVP@C) cathode material shows a good rate capability, and long cycle life (89% capacity retention after 5000 cycles at a rate of 10C) with an ionic liquid electrolyte for room temperature sodium metal batteries. The electrochemical performance of a full-cell sodium ion battery with NVP@C and hard carbon electrodes was also investigated at room temperature with an ionic liquid electrolyte. The battery exhibited 368 W h kg-1 energy density and 75% capacity retention after 100 cycles, outperforming the organic electrolyte-based devices.

Impact of Cl Doping on Electrochemical Performance in Orthosilicate (Li2FeSiO4): A Density Functional Theory Supported Experimental Approach.

Safe and high-capacity cathode materials are a long quest for commercial lithium-ion battery development. Among various searched cathode materials, Li2FeSiO4 has taken the attention due to optimal working voltage, high elemental abundance, and low toxicity. However, as per our understanding and observation, the electrochemical performance of this material is significantly limited by the intrinsic low electronic conductivity and slow lithium-ion diffusion, which limits the practical capacity (a theoretical value of ∼330 mAh g-1). In this report, using first-principles density functional theory based approach, we demonstrate that chlorine doping on oxygen site can enhance the electronic conductivity of the electrode and concurrently improve the electrochemical performance. Experimentally, X-ray diffraction, X-ray photoelectron spectroscopy, and field-emission gun scanning electron microscopy elemental mapping confirms Cl doping in Li2-xFeSiO4-xClx/C (x ≤ 0.1), while electrochemical cycling performance demonstrated improved performance. The theoretical and experimental studies collectively predict that, via Cl doping, the lithium deinsertion voltage associated with the Fe2+/Fe3+ and Fe3+/Fe4+ redox couples can be reduced and electronic conductivity can be enhanced, which opens up the possibility of utilization of silicate-based cathode with carbonate-based commercial electrolyte. In view of potential and electronic conductivity benefits, our results indicate that Cl doping can be a promising low-cost method to improve the electrochemical performance of silicate-based cathode materials.

A Facile Bottom-Up Approach to Construct Hybrid Flexible Cathode Scaffold for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur batteries mostly suffer from the low utilization of sulfur, poor cycle life, and low rate performances. The prime factors that affect the performance are enormous volume change of the electrode, soluble intermediate product formation, poor electronic and ionic conductivity of S, and end discharge products (i.e., Li2S2 and Li2S). The attractive way to mitigate these challenges underlying in the fabrication of a sulfur nanocomposite electrode consisting of different nanoparticles with distinct properties of lithium storage capability, mechanical reinforcement, and ionic as well as electronic conductivity leading to a mechanically robust and mixed conductive (ionic and electronic conductive) sulfur electrode. Herein, we report a novel bottom-up approach to synthesize a unique freestanding, flexible cathode scaffold made of porous reduced graphene oxide, nanosized sulfur, and Mn3O4 nanoparticles, and all are three-dimensionally interconnected to each other by hybrid polyaniline/sodium alginate (PANI-SA) matrix to serve individual purposes. A capacity of 1098 mAh g-1 is achieved against lithium after 200 cycles at a current rate of 2 A g-1 with 97.6% of initial capacity at a same current rate, suggesting the extreme stability and cycling performance of such electrode. Interestingly, with the higher current density of 5 A g-1, the composite electrode exhibited an initial capacity of 1015 mA h g-1 and retained 71% of the original capacity after 500 cycles. The in situ Raman study confirms the polysulfide absorption capability of Mn3O4. This work provides a new strategy to design a mechanically robust, mixed conductive nanocomposite electrode for high-performance lithium-sulfur batteries and a strategy that can be used to develop flexible large power storage devices.

Sustainable Sulfur-rich Copolymer/Graphene Composite as Lithium-Sulfur Battery Cathode with Excellent Electrochemical Performance.

A sulfur-rich copolymer, poly(S-r-C-a) has been synthesized via a sustainable route, showing the utility of two major industrial wastes- elemental sulfur (petroleum waste) and cardanol (agro waste), to explore its potential as cathode material for Li-S batteries. The sulfur-rich copolymer exhibited a reduction in the active material dissolution into the electrolyte and a low self-discharge rate behavior during the rest time compared to an elemental sulfur cathode, indicating the chemical confinement of sulfur units. The presence of organosulfur moieties in copolymer suppress the irreversible deposition of end-discharge products on electrode surfaces and thus improve the electrochemical performances of Li-S batteries. This sulfur copolymer offered a reversible capacity of 892 mA h g(-1) at 2nd cycle and maintained the capacity of 528 mA h g(-1) after 50 cycles at 200 mA g(-1). Reduced graphene oxide (rGO) prepared via a sustainable route was used as a conductive filler to extract the better electrochemical performances from this sulfur copolymer. Such sustainable origin batteries prepared via economically viable showed an improved specific capacity of ~975 mA h g(-1) after 100 cycles at 200 mA g(-1) current rate with capacity fading of 0.15% per cycle and maintained a stable performance over 500 cycles at 2000 mA g(-1).

Rechargeable Sodium-Ion Battery: High-Capacity Ammonium Vanadate Cathode with Enhanced Stability at High Rate.

Sodium-ion battery (NIB) cathode performance based on ammonium vanadate is demonstrated here as having high capacity, long cycle life and good rate capability. The simple preparation process and morphology study enable us to explore this electrode as suitable NIB cathode. Furthermore, density functional theory (DFT) calculation is envisioned for the NH4V4O10 cathode, and three possible sodium arrangements in the structure are depicted for the first time. Relevant NIB-related properties such as average voltage, lattice constants, and atomic coordinates have been derived, and the estimated values are in good agreement with the current experimental values. A screening study shows ammonium vanadate electrodes prepared on carbon coat onto Al-current collector exhibits a better electrochemical performance toward sodium, with a sustained reversible capacity and outstanding rate capability. With the current cathode with nanobelt morphology, a reversible capacity of 190 mAh g(-1) is attained at a charging rate of 200 mA g(-1), and a stable capacity of above 120 mAh g(-1) is retained for an extended 50 cycles tested at 1000 mA g(-1) without the addition of any expensive electrolyte additive.

Exfoliated MoS2 Sheets and Reduced Graphene Oxide-An Excellent and Fast Anode for Sodium-ion Battery.

Three dimensional (3D) MoS2 nanoflowers are successfully synthesized by hydrothermal method. Further, a composite of as prepared MoS2 nanoflowers and rGO is constructed by simple ultrasonic exfoliation technique. The crystallography and morphological studies have been carried out by XRD, FE-SEM, TEM, HR-TEM and EDS etc. Here, XRD study revealed, a composite of exfoliated MoS2 with expanded spacing of (002) crystal plane and rGO can be prepared by simple 40 minute of ultrasonic treatment. While, FE-SEM and TEM studies depict, individual MoS2 nanoflowers with an average diameter of 200 nm are uniformly distributed throughout the rGO surface. When tested as sodium-ion batteries anode material by applying two different potential windows, the composite demonstrates a high reversible specific capacity of 575 mAhg(-1) at 100 mAg(-1) in between 0.01 V-2.6 V and 218 mAhg(-1) at 50 mAg(-1) when discharged in a potential range of 0.4 V-2.6 V. As per our concern, the results are one of the best obtained as compared to the earlier published one on MoS2 based SIB anode material and more importantly this material shows such an excellent reversible Na-storage capacity and good cycling stability without addition of any expensive additive stabilizer, like fluoroethylene carbonate (FEC), in comparison to those in current literature.

Atomic layer deposited tungsten nitride thin films as a new lithium-ion battery anode.

This article demonstrates the atomic layer deposition (ALD) of tungsten nitride using tungsten hexacarbonyl [W(CO)6] and ammonia [NH3] and its use as a lithium-ion battery anode. In situ quartz crystal microbalance (QCM), ellipsometry and X-ray reflectivity (XRR) measurements are carried out to confirm the self-limiting behaviour of the deposition. A saturated growth rate of ca. 0.35 Å per ALD cycle is found within a narrow temperature window of 180-195 °C. In situ Fourier transform infrared (FTIR) vibrational spectroscopy is used to determine the reaction pathways of the surface bound species after each ALD half cycle. The elemental presence and chemical composition is determined by XPS. The as-deposited material is found to be amorphous and crystallized to h-W2N upon annealing at an elevated temperature under an ammonia atmosphere. The as-deposited materials are found to be n-type, conducting with an average carrier concentration of ca. 10(20) at room temperature. Electrochemical studies of the as-deposited films open up the possibility of this material to be used as an anode material in Li-ion batteries. The incorporation of MWCNTs as a scaffold layer further enhances the electrochemical storage capacity of the ALD grown tungsten nitride (WNx). Ex situ XRD analysis confirms the conversion based reaction mechanism of the as-grown material with Li under operation.

Flagellar filament bio-templated inorganic oxide materials - towards an efficient lithium battery anode.

Designing a new generation of energy-intensive and sustainable electrode materials for batteries to power a variety of applications is an imperative task. The use of biomaterials as a nanosized structural template for these materials has the potential to produce hitherto unachievable structures. In this report, we have used genetically modified flagellar filaments of the extremely halophilic archaea species Halobacterium salinarum to synthesize nanostructured iron oxide composites for use as a lithium-ion battery anode. The electrode demonstrated a superior electrochemical performance compared to existing literature results, with good capacity retention of 1032 mAh g(-1) after 50 cycles and with high rate capability, delivering 770 mAh g(-1) at 5 A g(-1) (~5 C) discharge rate. This unique flagellar filament based template has the potential to provide access to other highly structured advanced energy materials in the future.

An experimental and computational study to understand the lithium storage mechanism in molybdenum disulfide.

The lithium storage mechanism in molybdenum disulfide (MoS(2)) has been comprehensively investigated as the existing conversion-based storage mechanism is unable to explain the reason behind its high practical capacity, high polarization losses, and the change in the discharge profile after the 1(st) charge-discharge cycle. To resolve these issues and to gain a deeper understanding of MoS(2)-based Li-ion batteries, for the first time, we have studied the reaction mechanism of the MoS(2) anode using various experimental techniques such as XRD, Raman spectroscopy, electrochemical impedance spectroscopy, XANES, and EXAFS, as well as ab initio density functional theory based calculations. On the basis of the results presented here, and in line with some experimental findings, we find that the reaction of MoS(2) with Li is not as simple as with usual metal oxide based conversion reactions, but that the pathway of the conversion reaction changes after the first discharge process. In the first discharge process, lithiation is initiated by a limited intercalation process, followed by a conversion reaction that produces molybdenum nanoparticles (Mo) and lithium sulfide (Li(2)S). Whereas, unlike oxide-based conversion materials, MoS(2) does not transverse back during the delithiation process. Indeed, instead of MoS(2) formation, we identified the presence of polysulfur after the complete cycle. In consecutive cycles, polysulfur reacts with lithium and forms Li(2)S/Li(2)S(2), and this Li-S reaction is found to be highly reversible in nature and the only source of the high practical capacity observed in this electrode. To validate our experimental findings, an atomic scale ab initio computational study was also carried out, which likewise suggests that Li first intercalates between the MoS(2) layers but that after a certain concentration, it reacts with MoS(2) to form Li(2)S. The calculations also support the non-reversibility of the conversion reaction, by showing that Mo + Li(2)S formation is energetically more favorable than the re-formation of MoS(2) + Li.