Zhaoxin Yu

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.

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.

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.

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.

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.

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.

Flexible freestanding sandwich-structured sulfur cathode with superior performance for lithium–sulfur batteries

Flexible freestanding sandwich-structured sulfur cathodes are developed for lithium–sulfur batteries, which exhibit excellent cycling stability and rate capability. Moreover, a high areal capacity of ∼4 mA h cm−2 is demonstrated based on this new cathode configuration with high sulfur loading (∼4 mg S cm−2).

Exceptionally High Ionic Conductivity in Na3P0.62As0.38S4 with Improved Moisture Stability for Solid-State Sodium-Ion Batteries

A Na-ion solid-state electrolyte, Na3 P0.62 As0.38 S4 , is developed with an exceptionally high conductivity of 1.46 mS cm-1 at 25 °C and enhanced moisture stability. Dual effects of alloying element As (lattice expansion and a weaker AsS bond strength) are responsible for the superior conductivity. Improved moisture stability is regulated by shifting low-energy moisture reactions to high-energy ones due to As.

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.