Advanced Sulfur Cathode Enabled by Highly Crumpled Nitrogen-Doped Graphene Sheets for High-Energy-Density Lithium-Sulfur Batteries.

Herein, we report a synthesis of highly crumpled nitrogen-doped graphene sheets with ultrahigh pore volume (5.4 cm(3)/g) via a simple thermally induced expansion strategy in absence of any templates. The wrinkled graphene sheets are interwoven rather than stacked, enabling rich nitrogen-containing active sites. Benefiting from the unique pore structure and nitrogen-doping induced strong polysulfide adsorption ability, lithium-sulfur battery cells using these wrinkled graphene sheets as both sulfur host and interlayer achieved a high capacity of ∼1000 mAh/g and exceptional cycling stability even at high sulfur content (≥80 wt %) and sulfur loading (5 mg sulfur/cm(2)). The high specific capacity together with the high sulfur loading push the areal capacity of sulfur cathodes to ∼5 mAh/cm(2), which is outstanding compared to other recently developed sulfur cathodes and ideal for practical applications.

Functional Organosulfide Electrolyte Promotes an Alternate Reaction Pathway to Achieve High Performance in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have recently received great attention because they promise to provide energy density far beyond current lithium ion batteries. Typically, Li-S batteries operate by conversion of sulfur to reversibly form different soluble lithium polysulfide intermediates and insoluble lithium sulfides through multistep redox reactions. Herein, we report a functional electrolyte system incorporating dimethyl disulfide as a co-solvent that enables a new electrochemical reduction pathway for sulfur cathodes. This pathway uses soluble dimethyl polysulfides and lithium organosulfides as intermediates and products, which can boost cell capacity and lead to improved discharge-charge reversibility and cycling performance of sulfur cathodes. This electrolyte system can potentially enable Li-S batteries to achieve high energy density.

Chemically bonded phosphorus/graphene hybrid as a high performance anode for sodium-ion batteries.

Room temperature sodium-ion batteries are of great interest for high-energy-density energy storage systems because of low-cost and natural abundance of sodium. Here, we report a novel phosphorus/graphene nanosheet hybrid as a high performance anode for sodium-ion batteries through facile ball milling of red phosphorus and graphene stacks. The graphene stacks are mechanically exfoliated to nanosheets that chemically bond with the surfaces of phosphorus particles. This chemical bonding can facilitate robust and intimate contact between phosphorus and graphene nanosheets, and the graphene at the particle surfaces can help maintain electrical contact and stabilize the solid electrolyte interphase upon the large volume change of phosphorus during cycling. As a result, the phosphorus/graphene nanosheet hybrid nanostructured anode delivers a high reversible capacity of 2077 mAh/g with excellent cycling stability (1700 mAh/g after 60 cycles) and high Coulombic efficiency (>98%). This simple synthesis approach and unique nanostructure can potentially be applied to other phosphorus-based alloy anode materials for sodium-ion batteries.

Strong lithium polysulfide chemisorption on electroactive sites of nitrogen-doped carbon composites for high-performance lithium-sulfur battery cathodes.

Despite the high theoretical capacity of lithium-sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g(-1) after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer-sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm(-2)) with a high sulfur loading of approximately 5 mg cm(-2), which is ideal for practical applications of the lithium-sulfur batteries.

Polyanthraquinone as a Reliable Organic Electrode for Stable and Fast Lithium Storage.

In spite of recent progress, there is still a lack of reliable organic electrodes for Li storage with high comprehensive performance, especially in terms of long-term cycling stability. Herein, we report an ideal polymer electrode based on anthraquinone, namely, polyanthraquinone (PAQ), or specifically, poly(1,4-anthraquinone) (P14AQ) and poly(1,5-anthraquinone) (P15AQ). As a lithium-storage cathode, P14AQ showed exceptional performance, including reversible capacity almost equal to the theoretical value (260 mA h g(-1); >257 mA h g(-1) for AQ), a very small voltage gap between the charge and discharge curves (2.18-2.14=0.04 V), stable cycling performance (99.4% capacity retention after 1000 cycles), and fast-discharge/charge ability (release of 69% of the low-rate capacity or 64% of the energy in just 2 min). Exploration of the structure-performance relationship between P14AQ and related materials also provided us with deeper understanding for the design of organic electrodes.

Polymer-graphene nanocomposites as ultrafast-charge and -discharge cathodes for rechargeable lithium batteries.

Electroactive polymers are a new generation of "green" cathode materials for rechargeable lithium batteries. We have developed nanocomposites combining graphene with two promising polymer cathode materials, poly(anthraquinonyl sulfide) and polyimide, to improve their high-rate performance. The polymer-graphene nanocomposites were synthesized through a simple in situ polymerization in the presence of graphene sheets. The highly dispersed graphene sheets in the nanocomposite drastically enhanced the electronic conductivity and allowed the electrochemical activity of the polymer cathode to be efficiently utilized. This allows for ultrafast charging and discharging; the composite can deliver more than 100 mAh/g within just a few seconds.

Silicon core-hollow carbon shell nanocomposites with tunable buffer voids for high capacity anodes of lithium-ion batteries.

Silicon core-hollow carbon shell nanocomposites with controllable voids between silicon nanoparticles and hollow carbon shell were easily synthesized by a two-step coating method and exhibited different charge-discharge cyclability as anodes for lithium-ion batteries. The best capacity retention can be achieved with a void/Si volume ratio of approx. 3 due to its appropriate volume change tolerance and maintenance of good electrical contacts.

Minimized Volume Expansion in Hierarchical Porous Silicon upon Lithiation.

Silicon (Si) remains one of the most promising anode materials for next-generation lithium-ion batteries (LIBs). The key challenge for Si anodes is the huge volume change during lithiation-delithiation cycles that leads to electrode pulverization and rapid capacity fading. Here, we report a hierarchical porous Si (hp-Si) with a tailored porous structure [tunable primary pores (20-200 nm) and secondary nanopores (∼3-10 nm)] that can effectively minimize the volume expansion. An in situ transmission electron microscopy (TEM) study revealed that the hp-Si material with the same porosity but larger primary pores can more effectively accommodate lithiation-induced volume expansion, giving rise to a much reduced apparent volume expansion on both material and electrode levels. Chemomechanical modeling revealed that because of the different relative stiffnesses of the lithiated and unlithiated Si phases, the primary pore size plays a key role in accommodating the volume expansion of lithiated Si. The higher structural stability of the hp-Si materials with larger primary pores also maintains the fast diffusion channels of the connective pores, giving rise to better power capability and capacity retention upon electrochemical cycling. Our findings point toward an optimized hp-Si material with minimal volume change during electrochemical cycling for next-generation LIBs.

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries.

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this work, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retention of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. By coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ∼3 mAh cm-2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ∼1000 mAh g-1 and an excellent capacity retention of >65% after 450 cycles at C/10.

Integrating Si nanoscale building blocks into micro-sized materials to enable practical applications in lithium-ion batteries.

This article highlights recent advances in micro-sized silicon anode materials composed of silicon nanoscale building blocks for lithium-ion batteries. These materials show great potential in practical applications since they combine good cycling stability, high rate performance, and high volumetric capacity. Different preparation methods are introduced and the features and performance of the resulting materials are discussed. Key take-away points are interspersed through the discussion, including comments on the roles of the nanoscale building blocks. Finally, we discuss current challenges and provide an outlook for future development of micro-sized silicon-based anode materials.

Self-Templated Synthesis of Mesoporous Carbon from Carbon Tetrachloride Precursor for Supercapacitor Electrodes.

A high-surface-area mesoporous carbon material has been synthesized using a self-templating approach via reduction of carbon tetrachloride by sodium potassium alloy. The advantage is the reduction-generated salt templates can be easily removed with just water. The produced mesoporous carbon has a high surface area and a narrow pore size distribution. When used as a supercapacitor electrode, this material exhibits a high specific capacitance (259 F g(-1)) and excellent cycling performance (>92% capacitance retention for 6000 cycles).

Advanced Sodium Ion Battery Anode Constructed via Chemical Bonding between Phosphorus, Carbon Nanotube, and Cross-Linked Polymer Binder.

Maintaining structural stability is a great challenge for high-capacity conversion electrodes with large volume change but is necessary for the development of high-energy-density, long-cycling batteries. Here, we report a stable phosphorus anode for sodium ion batteries by the synergistic use of chemically bonded phosphorus-carbon nanotube (P-CNT) hybrid and cross-linked polymer binder. The P-CNT hybrid was synthesized through ball-milling of red phosphorus and carboxylic group functionalized carbon nanotubes. The P-O-C bonds formed in this process help maintain contact between phosphorus and CNTs, leading to a durable hybrid. In addition, cross-linked carboxymethyl cellulose-citric acid binder was used to form a robust electrode. As a result, this anode delivers a stable cycling capacity of 1586.2 mAh/g after 100 cycles, along with high initial Coulombic efficiency of 84.7% and subsequent cycling efficiency of ∼99%. The unique electrode framework through chemical bonding strategy reported here is potentially inspirable for other electrode materials with large volume change in use.

Phosphorus-Graphene Nanosheet Hybrids as Lithium-Ion Anode with Exceptional High-Temperature Cycling Stability.

A red phosphorus-graphene nanosheet hybrid is reported as an anode material for lithium-ion batteries. Graphene nanosheets form a sea-like, highly electronically conductive matrix, where the island-like phosphorus particles are dispersed. Benefiting from this structure and properties of phosphorus, the hybrid delivers high initial capacity and exhibits promising retention at 60 °C.

Understanding the effect of a fluorinated ether on the performance of lithium-sulfur batteries.

A high performance Li-S battery with novel fluoroether-based electrolyte was reported. The fluorinated electrolyte prevents the polysulfide shuttling effect and improves the Coulombic efficiency and capacity retention of the Li-S battery. Reversible redox reaction of the sulfur electrode in the presence of fluoroether TTE was systematically investigated. Electrochemical tests and post-test analysis using HPLC, XPS, and SEM/EDS were performed to examine the electrode and the electrolyte after cycling. The results demonstrate that TTE as a cosolvent mitigates polysulfide dissolution and promotes conversion kinetics from polysulfides to Li2S/Li2S2. Furthermore, TTE participates in a redox reaction on both electrodes, forming a solid electrolyte interphase (SEI) which further prevents parasitic reactions and thus improves the utilization of the active material.

Bottom-up synthesis of high surface area mesoporous crystalline silicon and evaluation of its hydrogen evolution performance.

As an important material for many practical and research applications, porous silicon has attracted interest for decades. Conventional preparations suffer from high mass loss because of their etching nature. A few alternative routes have been reported, including magnesiothermic reduction; however, pre-formed porous precursors are still necessary, leading to complicated syntheses. Here we demonstrate a bottom-up synthesis of mesoporous crystalline silicon materials with high surface area and tunable primary particle/pore size via a self-templating pore formation process. The chemical synthesis utilizes salt by-products as internal self-forming templates that can be easily removed without any etchants. The advantages of these materials, such as their nanosized crystalline primary particles and high surface areas, enable increased photocatalytic hydrogen evolution rate and extended working life. These also make the mesoporous silicon a potential candidate for other applications, such as optoelectronics, drug delivery systems and even lithium-ion batteries.

Bis(2,2,2-trifluoroethyl) ether as an electrolyte co-solvent for mitigating self-discharge in lithium-sulfur batteries.

Lithium-sulfur batteries suffer from severe self-discharge because of polysulfide dissolution and side reaction. In this work, a novel electrolyte containing bis(2,2,2-trifluoroethyl) ether (BTFE) was used to mitigate self-discharge of Li-S cells having both low- and high-sulfur-loading sulfur cathodes. This electrolyte meaningfully decreased self-discharge at elevated temperature, though differences in behavior of cells with high- and low-sulfur-loading were also noted. Further investigation showed that this effect likely stems from the formation of a more robust protective film on the anode surface.

Porous spherical carbon/sulfur nanocomposites by aerosol-assisted synthesis: the effect of pore structure and morphology on their electrochemical performance as lithium/sulfur battery cathodes.

Porous spherical carbons (PSCs) with tunable pore structure (pore volume, pore size, and surface area) were prepared by an aerosol-assisted process. PSC/sulfur composites (PSC/S, S: ca.59 wt %) were then made and characterized as cathodes in lithium/sulfur batteries. The relationships between the electrochemical performance of PSC/S composites and their pore structure and particle morphology were systematically investigated. PSC/S composite cathodes with large pore volume (>2.81 cm(3)/g) and pore size (>5.10 nm) were found to exhibit superior electrochemical performance, likely due to better mass transport in the cathode. In addition, compared with irregularly shaped carbon/sulfur composite, the spherical shaped PSC/S composite showed better performance due to better electrical contact among the particles.

Mesoporous carbon-carbon nanotube-sulfur composite microspheres for high-areal-capacity lithium-sulfur battery cathodes.

Lithium-sulfur (Li-S) batteries offer theoretical energy density much higher than that of lithium-ion batteries, but their development faces significant challenges. Mesoporous carbon-sulfur composite microspheres are successfully synthesized by combining emulsion polymerization and the evaporation-induced self-assembly (EISA) process. Such materials not only exhibit high sulfur-specific capacity and excellent retention as Li-S cathodes but also afford much improved tap density, sulfur content, and areal capacity necessary for practical development of high-energy-density Li-S batteries. In addition, when incorporated with carbon nanotubes (CNTs) to form mesoporous carbon-CNT-sulfur composite microspheres, the material demonstrated superb battery performance even at a high current density of 2.8 mA/cm(2), with a reversible capacity over 700 mAh/g after 200 cycles.