Reconstructable Carbon Monolayer-MoS2 Intercalated Heterostructure Enabled by Atomic Layers-Confined Topotactic Transformation for Ultrafast Lithium Storage.

The intercalation structure of two-dimensional materials with expanded interlayer distance can facilitate mass transport, which is promising in fast-charging lithium-ion batteries (LIBs). However, the designed intercalation structures will be pulverized and destroyed under tough working conditions, causing overall performance deterioration of the batteries. Here, we present that an intercalated heterostructure made of the typical layered material of MoS2 intercalated by N-doped graphene-like carbon monolayer (MoS2/g-CM) through a polymer intercalation strategy exhibits a unique behavior of reversible reconstructability as an LIB anode during cycling. A mechanism of "carbon monolayers-confined topotactic transformation" is proposed, which is evidenced by substantial in/ex situ characterizations. The intercalated heterostructure of MoS2/g-CM featuring a reconstructable property and efficient interlayer electron/ion transport exhibits an unprecedented rate capability up to 50 A g-1 and outstanding long cyclability. Moreover, the proposed strategy based on g-CM intercalation has been extended to the MoSe2 system, also realizing reconstructability of the intercalated heterostructure and improved LIB performance, demonstrating its versatility and great potential in applications.

A Radical Pathway and Stabilized Li Anode Enabled by Halide Quaternary Ammonium Electrolyte Additives for Lithium-Sulfur Batteries.

Passivation of the sulfur cathode by insulating lithium sulfide restricts the reversibility and sulfur utilization of Li-S batteries. 3D nucleation of Li2 S enabled by radical conversion may significantly boost the redox kinetics. Electrolytes with high donor number (DN) solvents allow for tri-sulfur (S3 ⋅- ) radicals as intermediates, however, the catastrophic reactivity of such solvents with Li anodes pose a great challenge for their practical application. Here, we propose the use of quaternary ammonium salts as electrolyte additives, which can preserve the partial high-DN characteristics that trigger the S3 ⋅- radical pathway, and inhibit the growth of Li dendrites. Li-S batteries with tetrapropylammonium bromide (T3Br) electrolyte additive deliver the outstanding cycling stability (700 cycles at 1 C with a low-capacity decay rate of 0.049 % per cycle), and high capacity under a lean electrolyte of 5 µLelectrolyte mgsulfur -1 . This work opens a new avenue for the development of electrolyte additives for Li-S batteries.

Electrolyte Solvation Chemistry for the Solution of High-Donor-Number Solvent for Stable Li-S Batteries.

Passivation of the sulfur electrode by insulating lithium sulfide (Li2 S) restricts the reversibility and sulfur utilization of lithium-sulfur (Li-S) batteries. Although electrolytes with high donor number (DN) solvents induce tri-sulfur radical intermediate thus 3D nucleation of Li2 S with fast kinetics can be achieved, their catastrophic reactivities with Li metal hinder practical applications. Here, the use of high DN solvent as an additive instead of as co-solvent to solve their incompatibility between cathode and anode is proposed, by adopting N-methyl-2-pyrrolidone (NMP) as a proof-of-concept. Such a strategy is accomplished by the unique solvation structure of the NMP added electrolyte, where the preference of NMP-Li+ coordination squeezes out partial 1,2-dimethoxyethane (DME) molecules while enriching 1,3-dioxolane (DOL) molecules in the first solvation sheath of Li+ ions. It affords the robust SEI on Li metal from corrosion either by NMP or the dissolved polysulfides. Spectral analyses (Raman and UV-vis) also verify that the coordinated NMP additive preserves its S3 •- radicals stabilization ability as it does as a co-solvent, which effectively improves the sulfur conversion kinetics and reversibility. This approach enables competitive capacity retention and a stable cycling performance of 340 cycles, which is one of the longest lifespans known for the high DN solvent involved Li-S batteries.

Size-Dependent Cobalt Catalyst for Lithium Sulfur Batteries: From Single Atoms to Nanoclusters and Nanoparticles.

The sulfur redox conversion with catalytically improved kinetics is promising to mitigate the polysulfides shuttling. While the size of electrocatalyst always brings different catalytic behaviors for various heterogeneous catalytic reactions, it is yet to be explored for Li-S batteries. Herein, a systematical study of size-dependent catalytic activity toward polysulfides conversion and the relevance to electrochemical performance are reported, by constructing Co catalysts with different atomic scales from single atoms, atomic clusters to nanoparticles. Fundamental electrocatalytic studies are focused by probing the reduction kinetics and activation energies of sulfur chemistry. The single atomic Co shows the best charge transfer/kinetic toward sulfur redox, especially for the rate-determining reaction (Li2 S4  â†” Li2 S) as demonstrated by the significantly lowered energy barrier for Li2 S nucleation/dissolution. This is owing to stronger geometric deformation of the catalyst with lower aggregation extent when it interacts with sulfur species, thus leading to decreased Gibbs free energy changes as elucidated by DFT calculations. The superior catalytic activity of single atomic Co promises a high specific capacity (4.98 mAh cm-2 ) at an areal loading of 4.3 mg cm-2 over long-term cycling. The finding emphasizes the significance of the size-dependent catalytic activity to the reaction kinetics and the overall performance of Li-S batteries.

Armoring Black Phosphorus Anode with Stable Metal-Organic-Framework Layer for Hybrid K-Ion Capacitors.

Potassium-ion capacitors (KICs) are promising for sustainable and eco-friendly energy storage technologies, yet their slow reaction kinetics and poor cyclability induced by large K-ion size are a major obstacle toward practical applications. Herein, by employing black phosphorus nanosheets (BPNSs) as a typical high-capacity anode material, we report that BPNS anodes armored with an ultrathin oriented-grown metal-organic-framework (MOF) interphase layer (BPNS@MOF) exhibit regulated potassium storage behavior for high-performance KICs. The MOF interphase layers as protective layer with ordered pores and high chemical/mechanical stability facilitate K ion diffusion and accommodate the volume change of electrode, beneficial for improved reaction kinetics and enhanced cyclability, as evidenced by substantial characterizations, kinetics analysis and DFT calculations. Consequently, the BPNS@MOF electrode as KIC anodes exhibits outstanding cycle performance outperforming most of the reported state-of-art KICs so far.

CoPSe: A New Ternary Anode Material for Stable and High-Rate Sodium/Potassium-Ion Batteries.

The exploration of ideal electrode materials overcoming the critical problems of large electrode volume changes and sluggish redox kinetics induced by large ionic radius of Na+ /K+ ions is highly desirable for sodium/potassium-ion batteries (SIBs/PIBs) toward large-scale applications. The present work demonstrates that single-phase ternary cobalt phosphoselenide (CoPSe) in the form of nanoparticles embedded in a layered metal-organic framework (MOF)-derived N-doped carbon matrix (CoPSe/NC) represents an ultrastable and high-rate anode material for SIBs/PIBs. The CoPSe/NC is fabricated by using the MOF as both a template and precursor, coupled with in situ synchronous phosphorization/selenization reactions. The CoPSe anode holds a set of intrinsic merits such as lower mechanical stress, enhanced reaction kinetics, as well as higher theoretical capacity and lower discharge voltage relative to its counterpart of CoSe2 , and suppressed shuttle effect with higher intrinsic electrical conductivity relative to CoPS. The involved mechanisms are evidenced by substantial characterizations and density functional theory (DFT) calculations. Consequently, the CoPSe/NC anode shows an outstanding long-cycle stability and rate performance for SIBs and PIBs. Moreover, the CoPSe/NC-based Na-ion full cell can achieve a higher energy density of 274 Wh kg-1 , surpassing that based on CoSe2 /NC and most state-of-the-art Na-ion full cells based on P-, Se-, or S-containing binary/ternary anodes to date.

Covalent Assembly of MoS2 Nanosheets with SnS Nanodots as Linkages for Lithium/Sodium-Ion Batteries.

Weak van der Waals interactions between interlayers of two-dimensional layered materials result in disabled across-interlayer electron transfer and poor layered structural stability, seriously deteriorating their performance in energy applications. Herein, we propose a novel covalent assembly strategy for MoS2 nanosheets to realize unique MoS2 /SnS hollow superassemblies (HSs) by using SnS nanodots as covalent linkages. The covalent assembly based on all-inorganic and carbon-free concept enables effective across-interlayer electron transfer, facilitated ion diffusion kinetics, and outstanding mechanical stability, which are evidenced by experimental characterization, DFT calculations, and mechanical simulations. Consequently, the MoS2 /SnS HSs exhibit superb rate performance and long cycling stability in lithium-ion batteries, representing the best comprehensive performance in carbon-free MoS2 -based anodes to date. Moreover, the MoS2 /SnS HSs also show excellent sodium storage performance in sodium-ion batteries.

Comprehensive Design of the High-Sulfur-Loading Li-S Battery Based on MXene Nanosheets.

The lithium-sulfur battery is the subject of much recent attention due to the high theoretical energy density, but practical applications are challenged by fast decay owing to polysulfide shuttle and electrode architecture degradation. A comprehensive study of the sulfur host microstructure design and the cell architecture construction based on the MXene phase (Ti3C2Tx nanosheets) is performed, aiming at realize stable cycling performance of Li-S battery with high sulfur areal loading. The interwoven KB@Ti3C2Tx composite formed by self-assembly of MXene and Ktejen black, not only provides superior conductivity and maintains the electrode integrality bearing the volume expansion/shrinkage when used as the sulfur host, but also functions as an interlayer on separator to further retard the polysulfide cross-diffusion that possibly escaped from the cathode. The KB@Ti3C2Tx interlayer is only 0.28 mg cm-2 in areal loading and 3 µm in thickness, which accounts a little contribution to the thick sulfur electrode; thus, the impacts on the energy density is minimal. By coupling the robust KB@Ti3C2Tx cathode and the effective KB@Ti3C2Tx modified separator, a stable Li-S battery with high sulfur areal loading (5.6 mg cm-2) and high areal capacity (6.4 mAh cm-2) at relatively lean electrolyte is achieved.

Hybrid Anatase/Rutile Nanodots-Embedded Covalent Organic Frameworks with Complementary Polysulfide Adsorption for High-Performance Lithium-Sulfur Batteries.

The shuttling effect of polysulfides species seriously deteriorates the performance of Li-S batteries, representing the major obstacle for their practical use. However, the exploration of ideal cathodes that can suppress the shuttling of all polysulfides species is challenging. Herein, we propose an ingenious and effective strategy for constructing hybrid-crystal-phase TiO2/covalent organic framework (HCPT@COF) composites where hybrid anatase/rutile TiO2 nanodots (10 nm) are uniformly embedded in the interlayers of porous COFs. The synthesis was realized via a multiple-step reaction relay accompanying by a pseudo-topotactic transformation of three-dimensional layered structures from 1,4-dicyanobenzene monomer-embedded Ti-intermediate networks to HCPT nanodots-embedded COF frameworks. The HCPT@COF/S cathodes show superior comprehensive performance such as high specific capacity, long cycling stability, and remarkable rate capability for Li-S batteries, owing to the complementary anchoring effect of hybrid anatase/rutile TiO2 in the HCPT@COF composite, which is evidenced by substantial characterizations including X-ray photoelectron spectroscopy and density functional theory calculations.

A polymer-direct-intercalation strategy for MoS2/carbon-derived heteroaerogels with ultrahigh pseudocapacitance.

The intercalation strategy has become crucial for 2D layered materials to achieve desirable properties, however, the intercalated guests are often limited to metal ions or small molecules. Here, we develop a simple, mild and efficient polymer-direct-intercalation strategy that different polymers (polyethyleneimine and polyethylene glycol) can directly intercalate into the MoS2 interlayers, forming MoS2-polymer composites and interlayer-expanded MoS2/carbon heteroaerogels after carbonization. The polymer-direct-intercalation behavior has been investigated by substantial characterizations and molecular dynamic calculations. The resulting composite heteroaerogels possess 3D conductive MoS2/C frameworks, expanded MoS2 interlayers (0.98 nm), high MoS2 contents (up to 74%) and high Mo valence (+6), beneficial to fast and stable charge transport and enhanced pseudocapacitive energy storage. Consequently, the typical MoS2/N-doped carbon heteroaerogels exhibit outstanding supercapacitor performance, such as ultrahigh capacitance, remarkable rate capability and excellent cycling stability. This study offers a new intercalation strategy which may be generally applicable to 2D materials for promising energy applications.