Regenerative Solid Interfaces Enhance High-Performance All-Solid-State Lithium Batteries.

The performance of all-solid-state lithium batteries (ASSLBs) is significantly impacted by lithium interfacial instability, which originates from the dynamic chemical, morphological, and mechanical changes during deep Li plating and stripping. In this study, we introduce a facile approach to generate a conductive and regenerative solid interface, enhancing both the Li interfacial stability and overall cell performance. The regenerative interface is primarily composed of nanosized lithium iodide (nano-LiI), which originates in situ from the adopted solid-state electrolyte (SSE). During cell operation, the nano-LiI interfacial layer can reversibly diffuse back and forth in synchronization with Li plating and stripping. The interface and dynamic process improve the adhesion and Li+ transport between the Li anode and SSE, facilitating uniform Li plating and stripping. As a result, the metallic Li anode operates stably for over 1000 h at high current densities and even under elevated temperatures. By using metallic Li as the anode directly, we demonstrate stable cycling of all-solid-state Li-sulfur batteries for over 250 cycles at an areal capacity of >2 mA h cm-2 and room temperature. This study offers insights into the design of regenerative and Li+-conductive interfaces to tackle solid interfacial challenges for high-performance ASSLBs.

Enhancing Moisture Stability of Sulfide Solid-State Electrolytes by Reversible Amphipathic Molecular Coating.

The all-solid-state battery (ASSB) is a promising next-generation energy storage technology for both consumer electronics and electric vehicles because of its high energy density and improved safety. Sulfide solid-state electrolytes (SSEs) have merits of low density, high ionic conductivity, and favorable mechanical properties compared to oxide ceramic and polymer materials. However, mass production and processing of sulfide SSEs remain a grand challenge because of their poor moisture stability. Here, we report a reversible surface coating strategy for enhancing the moisture stability of sulfide SSEs using amphipathic organic molecules. An ultrathin layer of 1-bromopentane is coated on the sulfide SSE surface (e.g., Li7P2S8Br0.5I0.5) via Van der Waals force. 1-Bromopentane has more negative adsorption energy with SSEs than H2O based on first-principles calculations, thereby enhancing the moisture stability of SSEs because the hydrophobic long-chain alkyl tail of 1-bromopentane repels water molecules. Moreover, this amphipathic molecular layer has a negligible effect on ionic conductivity and can be removed reversibly by heating at low temperatures (e.g., 160 °C). This finding opens a new pathway for the surface engineering of moisture-sensitive SSEs and other energy materials, thereby speeding up their deployment in ASSBs.

Early Failure of Lithium-Sulfur Batteries at Practical Conditions: Crosstalk between Sulfur Cathode and Lithium Anode.

Lithium-sulfur (Li-S) batteries are one of the most promising next-generation energy storage technologies due to their high theoretical energy and low cost. However, Li-S cells with practically high energy still suffer from a very limited cycle life with reasons which remain unclear. Here, through cell study under practical conditions, it is proved that an internal short circuit (ISC) is a root cause of early cell failure and is ascribed to the crosstalk between the S cathode and Li anode. The cathode topography affects S reactions through influencing the local resistance and electrolyte distribution, particularly under lean electrolyte conditions. The inhomogeneous reactions of S cathodes are easily mirrored by the Li anodes, resulting in exaggerated localized Li plating/stripping, Li filament formation, and eventually cell ISC. Manipulating cathode topography is proven effective to extend the cell cycle life under practical conditions. The findings of this work shed new light on the electrode design for extending cycle life of high-energy Li-S cells, which are also applicable for other rechargeable Li or metal batteries.

Salt-Based Organic-Inorganic Nanocomposites: Towards A Stable Lithium Metal/Li10 GeP2 S12 Solid Electrolyte Interface.

Solid-state Li metal battery technology is attractive, owing to the high energy density, long lifespans, and better safety. A key obstacle in this technology is the unstable Li/solid-state electrolyte (SSE) interface involving electrolyte reduction by Li. Herein we report a novel approach based on the use of a nanocomposite consisting of organic elastomeric salts (LiO-(CH2 O)n -Li) and inorganic nanoparticle salts (LiF, -NSO2 -Li, Li2 O), which serve as an interphase to protect Li10 GeP2 S12 (LGPS), a highly conductive but reducible SSE. The nanocomposite is formed in situ on Li via the electrochemical decomposition of a liquid electrolyte, thus having excellent chemical and electrochemical stability, affinity for Li and LGPS, and limited interfacial resistance. XPS depth profiling and SEM show that the nanocomposite effectively restrained the reduction of LGPS. Stable Li electrodeposition over 3000 h and a 200 cycle life for a full cell were achieved.

Origin of Outstanding Phase and Moisture Stability in a Na3P1-xAsxS4 Superionic Conductor.

Sodium ion (Na) solid-state electrolytes (SSEs) are critical to address notorious safety issues associated with liquid electrolytes used in the current Na ion batteries. Fulfilling multiple innovations is a grand challenge but is imperative for advanced Na ion SSEs, such as a combination of high ionic conductivity and excellent chemical stability. Here, our first-principles and phonon calculations reveal that Na3P1-xAsxS4 (0 ≤ x ≤ 1) is a solid-state superionic conductor stabilized at 0 K by zero-point vibrational energy and at finite temperatures by vibrational and configurational entropies. Especially, our integrated first-principles and experimental approach indicates that Na3P1-xAsxS4 is dry-air stable. Additionally, the alloying element arsenic greatly enhances the moisture (i.e., H2O) stability of Na3P1-xAsxS4 by shifting the reaction products from the easy-forming oxysulfides (such as Na3POS3 and Na3PO2S2 with H2S release) to the difficult-forming hydrates (such as Na3P1-xAsxS4·nH2O with n = 8 and/or 9) due mainly to a weaker As-O affinity compared to that of P-O. The present work demonstrates that alloying is able to achieve multiple innovations for solid-state electrolytes, such as a desirable superionic conductor with not only a high ionic conductivity (for example, 1.46 mS/cm at room temperature achieved in Na3P0.62As0.38S4) but also an excellent chemical stability with respect to temperature, composition, and moisture.

Exceptionally High Ionic Conductivity in Na3 P0.62 As0.38 S4 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.

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.

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.

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.

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.

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.

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.

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.

Synthesis and transport property of Cu(1.8)S as a promising thermoelectric compound.

Polycrystalline Cu(1.8)S compounds were fabricated by using a combined process of mechanical alloying and spark plasma sintering. The Cu(1.8)S sample with a second Cu(1.96)S phase and a lot of micro pores shows its maximum ZT value 0.5 at 673 K which is the highest value for p-type sulfide thermoelectric materials so far.