High Safety Electrolyte Design for Enabling High Energy-Density System of LiNi0.8Co0.1Mn0.1O2//Phosphorus by Simultaneously Adjusting Dual Electrode/Electrolyte Interfaces.

The demand for state-of-the-art high-energy-density lithium-ion batteries is increasing. However, the low specific capacity of electrode materials in conventional full-cell systems cannot meet the requirements. Ni-rich layered oxide cathodes such as Li(Ni0.8Co0.1Mn0.1)O2 (NCM811) have a high theoretical specific capacity of 200 mAh g-1, but it is always accompanied by side reactions on the electrode/electrolyte interface. Phosphorus anode possesses a high theoretical specific capacity of 2596 mAh g-1, but it has a huge volume expansion (≈300%). Herein, a highly compatible and secure electrolyte is reported via introducing an additive with a narrow electrochemical window, Lithium difluoro(oxalato)borate (LiDFOB), into 1 m LiPF6 EC/DMC with tris (2,2,2-trifluoroethyl) phosphate (TFEP) as a cosolvent. LiDFOB participates in the formation of organic/inorganic hybrid electrode/electrolyte interface layers at both the cathode and anode sides. The side reactions on the surface of the NCM811 cathode and the volume expansion of the phosphorus anode are effectively alleviated. The NCM811//RP full cell in this electrolyte shows high capacity retention of 82% after 150 cycles at a 0.5C rate. Meanwhile, the electrolyte shows non-flammability. This work highlights the importance of manipulating the electrode/electrolyte interface layers for the design of lithium-ion batteries with high energy density.

A Molecularly Engineered Cathode Lithium Compensation Agent for High Energy Density Batteries.

Prelithiating cathode is considered as one of the most promising lithium compensation strategies for practical high energy density batteries. Whereas most of reported cathode lithium compensation agents are deficient owing to their poor air-stability, residual insulating solid, or formidable Li-extracting barrier. Here, this work proposes molecularly engineered 4-Fluoro-1,2-dihydroxybenzene Li salt (LiDF) with high specific capacity (382.7 mAh g-1 ) and appropriate delithiation potential (3.6-4.2 V) as an air-stable cathode Li compensation agent. More importantly, the charged residue 4-Fluoro-1,2-benzoquinone (BQF) can synergistically work as an electrode/electrolyte interface forming additive to build uniform and robust LiF-riched cathode/anode electrolyte interfaces (CEI/SEI). Consequently, less Li loss and retrained electrolyte decomposition are achieved. With 2 wt% 4-Fluoro-1,2-dihydroxybenzene Li salt initially blended within the cathode, 1.3 Ah pouch cells with NCM (Ni92) cathode and SiO/C (550 mAh g-1 ) anode can keep 91% capacity retention after 350 cycles at 1 C rate. Moreover, the anode free of NCM622+LiDF||Cu cell achieves 78% capacity retention after 100 cycles with the addition of 15 wt% LiDF. This work provides a feasible sight for the rational designing Li compensation agent at molecular level to realize high energy density batteries.

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High-Energy Li-S Batteries.

Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium-sulfur (Li-S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li-S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core-shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm-2 ) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm-2 ) with a low electrolyte/sulfur ratio (10 µL mg-1 ). This research further demonstrates a durable Li-Se/S pouch cell with high specific capacity, validating the potential practical applications.

Reversible Discharge Products in Li-Air Batteries.

Lithium-air (Li-air) batteries stand out among the post-Li-ion batteries due to their high energy density, which has rapidly progressed in the past years. Regarding the fundamental mechanism of Li-air batteries that discharge products produced and decomposed during charging and recharging progress, the reversibility of products closely affects the battery performance. Along with the upsurge of the mainstream discharge products lithium peroxide, with devoted efforts to screening electrolytes, constructing high-efficiency cathodes, and optimizing anodes, much progress is made in the fundamental understanding and performance. However, the limited advancement is insufficient. In this case, the investigations of other discharge products, including lithium hydroxide, lithium superoxide, lithium oxide, and lithium carbonate, emerge and bring breakthroughs for the Li-air battery technologies. To deepen the understanding of the electrochemical reactions and conversions of discharge products in the battery, recent advances in the various discharge products, mainly focusing on the growth and decomposition mechanisms and the determining factors are systematically reviewed. The perspectives for Li-air batteries on the fundamental development of discharge products and future applications are also provided.

A 3D Hierarchical Host with Enhanced Sodiophilicity Enabling Anode-Free Sodium-Metal Batteries.

Sodium-metal batteries (SMBs) are considered as a compliment to lithium-metal batteries for next-generation high-energy batteries because of their low cost and the abundance of sodium (Na). Herein, a 3D nanostructured porous carbon particle containing carbon-shell-coated Fe nanoparticles (PC-CFe) is employed as a highly reversible Na-metal host. PC-CFe has a unique 3D hierarchy based on sub-micrometer-sized carbon particles, ordered open channels, and evenly distributed carbon-coated Fe nanoparticles (CFe) on the surface. PC-CFe achieves high reversibility of Na plating/stripping processes over 500 cycles with a Coulombic efficiency of 99.6% at 10 mA cm-2 with 10 mAh cm-2 in Na//Cu asymmetric cells, as well as over 14 400 cycles at 60 mA cm-2 in Na//Na symmetric cells. Density functional theory calculations reveal that the superior cycling performance of PC-CFe stems from the stronger adsorption of Na on the surface of the CFe, providing initial nucleation sites more favorable to Na deposition. Moreover, the full cell with a PC-CFe host without Na metal and a high-loading Na3 V2 (PO4 )3 cathode (10 mg cm-2 ) maintains a high capacity of 103 mAh g-1 at 1 mA cm-2 even after 100 cycles, demonstrating the operation of anode-free SMBs.

A Flexible Aqueous Zinc-Iodine Microbattery with Unprecedented Energy Density.

Currently, reported aqueous microbatteries (MBs) only show unsatisfactory electrochemical performance (≤120 mWh cm-3 volumetric energy density and <1000 µWh cm-2 areal energy density) and it remains challenging to develop durable aqueous MBs that can simultaneously offer both high volumetric and areal energy density. Herein, an in situ electrodeposition strategy is adopted to construct a flexible aqueous zinc-iodine MB (ZIDMB). Notably, the fabrication process well avoids the use of common additives (such as binders, conductive agents, and toxic solvent) and also bypasses subsequent time-consuming procedures such as grinding, coating, drying, etc., thus greatly simplifying the manufacture of the ZIDMB. Meanwhile, owing to the suppression of the shuttle effect of triiodide ions and the high ionic conductivity of the polyelectrolyte, the ZIDMB can simultaneously deliver record-high volumetric and areal energy densities of 1647.3 mWh cm-3 and 2339.1 µWh cm-2 , thus achieving values at least 13.5- and 2.3-fold better than those of best available aqueous MBs, respectively. This work affords an innovative strategy to construct an ideal micro-power-source for future miniaturized and integrated electronics.

High-Safety and High-Energy-Density Lithium Metal Batteries in a Novel Ionic-Liquid Electrolyte.

Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, lithium metal batteries in a novel nonflammable ionic-liquid (IL) electrolyte composed of 1-ethyl-3-methylimidazolium (EMIm) cations and high-concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite-free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to ≈16 mg cm-2 . Li anodes paired with lithium cobalt oxide (LiCoO2 ) and lithium nickel cobalt manganese oxide (LiNi0.8 Co0.1 Mn0.1 O2 , NCM 811) cathodes exhibit 99.6-99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to ≈199 mAh g-1 and ≈765 Wh kg-1 respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li-NMC 811 full batteries.

Lithiophilic LiC6 Layers on Carbon Hosts Enabling Stable Li Metal Anode in Working Batteries.

Lithium (Li) metal-based battery is among the most promising candidates for next-generation rechargeable high-energy-density batteries. Carbon materials are strongly considered as the host of Li metal to relieve the powdery/dendritic Li formation and large volume change during repeated cycles. Herein, we describe the formation of a thin lithiophilic LiC6 layer between carbon fibers (CFs) and metallic Li in Li/CF composite anode obtained through a one-step rolling method. An electron deviation from Li to carbon elevates the negativity of carbon atoms after Li intercalation as LiC6 , which renders stronger binding between carbon framework and Li ions. The Li/CF | Li/CF batteries can operate for more than 90 h with a small polarization voltage of 120 mV at 50% discharge depth. The Li/CF | sulfur pouch cell exhibits a high discharge capacity of 3.25 mAh cm-2 and a large capacity retention rate of 98% after 100 cycles at 0.1 C. It is demonstrated that the as-obtained Li/CF composite anode with lithiophilic LiC6 layers can effectively alleviate volume expansion and hinder dendritic and powdery morphology of Li deposits. This work sheds fresh light on the role of interfacial layers between host structure and Li metal in composite anode for long-lifespan working batteries.