What Is the Real Origin of Single-Walled Carbon Nanotubes for the Performance Enhancement of Si-Based Anodes?

A large amount of lithium-ion storage in Si-based anodes promises high energy density yet also results in large volume expansion, causing impaired cyclability and conductivity. Instead of restricting pulverization of Si-based particles, herein, we disclose that single-walled carbon nanotubes (SWNTs) can take advantage of volume expansion and induce interfacial reactions that stabilize the pulverized Si-based clusters in situ. Operando Raman spectroscopy and density functional theory calculations reveal that the volume expansion by the lithiation of Si-based particles generates ∼14% tensile strains in SWNTs, which, in turn, strengthens the chemical interaction between Li and C. This chemomechanical coupling effect facilitates the transformation of sp2-C at the defect of SWNTs to Li-C bonds with sp3 hybridization, which also initiates the formation of new Si-C chemical bonds at the interface. Along with this process, SWNTs can also induce in situ reconstruction of the 3D architecture of the anode, forming mechanically strengthened networks with high electrical and ionic conductivities. As such, with the addition of only 1 wt % of SWNTs, graphite/SiOx composite anodes can deliver practical performance well surpassing that of commercial graphite anodes. These findings enrich our understanding of strain-induced interfacial reactions, providing a general principle for mitigating the degradation of alloying or conversion-reaction-based electrodes.

Directly Regenerating of Spent LiCoO2 with Gradient F-doped Subsurface towards Ultra-stable Storage Properties.

As great potential recycling strategy, the direct regeneration of spent LiCoO2 (LCO) is beneficial for lowering environmental pollutions and promoting global sustainability. However, owing to the using of binder and electrolyte, some fluorine impurities would be remained into spent materials. Considering the doping behaviors of F-elements, their suitable content introducing would facilitate the energy-storage abilities of regenerated LCO. Herein, through the tailored introduction of F-elements, spent LCO are successfully regenerated with physical-chemical evolutions. Benefitting from the existed oxygen vacancies, the diffusion energy-barrier of F-elements is reduced from 1.73 eV to 0.61 eV, facilitating the establishment of gradient F-doped subsurface, along with the formation of rigid CoO5F. Meanwhile, excess F-elements (1 wt.%, as a threshold) lead to the formation of LiF passivation layer on the surface. Thus, the as-optimized sample displays a considerable capacity of 154.4 mAh g-1 even at 5.0 C, with retention rate (88.3%) in 3.0~4.5V. Supported by detailed electrochemical and kinetic analysis, the structural advantages are confirmed to boost the improved redox activity of Co-ions and the alleviating of irreversible oxygen-release. Give this, the work is anticipated to reveal the evolutions of regenerated LCO with the introduced F-elements, whilst providing the practical regeneration strategies toward excellent high-voltage properties.

Strengthening and Toughening of ZG25SiMn2CrB Steel without Tempering Brittleness via Electropulsing Treatment.

High-strength low-alloy steels are widely used, but their traditional heat-treatment process is complex, energy-intensive, and makes it difficult to fully exploit the material's potential. In this paper, the electropulsing processing technology was applied to the quenching and tempering process of ZG25SiMn2CrB steel. Through microstructural characterization and mechanical property testing, the influence of electropulsing on the solid-state phase transition process of annealing steel was systematically studied. The heating process of the specimen with the annealing state (initial state) is the diffusion-type transition. As the discharge time increased, the microstructure gradually transformed from ferrite/pearlitic to slate martensite. Optimal mechanical properties and fine microstructure were achieved after quenching at 500 ms. The steel subjected to rapid tempering with 160 ms electropulsing exhibited good, comprehensive mechanical properties (tensile strength 1609 MPa, yield strength 1401.27 MPa, elongation 11.63%, and hardness 48.68 HRC). These favorable mechanical properties are attributed to the coupled impact of thermal and non-thermal effects induced by high-density pulse current. Specifically, the thermal effect provides the thermodynamic conditions for phase transformation, while the non-thermal effect reduces the nucleation barrier of austenite, which increases the nucleation rate during instantaneous heating, and the following rapid cooling suppresses the growth of austenite grains. Additionally, the fine microstructure prevents the occurrence of temper brittleness.

Encapsulation of Se into Cu-decorated MXene nanosheets with superior electrochemical performance for advanced Na-Se batteries.

Sodium-selenium (Na-Se) batteries are promising energy storage systems with high energy density, high safety, and low cost. However, the huge volume change of selenium, the dissolution shuttle of polyselenides, and low selenium loading need to be solved. Herein, Cu nanoparticles decorated MXene nanosheets composite (MXene/Cu) are synthesized by etching Ti3AlC2 using a molten salt etching strategy. The Se-loaded MXene/Cu (Se@MXene/Cu) electrode delivers superior electrochemical performance even with a high Se loading of ∼74.3 wt%, owing to the synergistic effect of the two-dimensional (2D) confined structure and catalytic role of the unique MXene/Cu host. Specifically, the obtained electrode provides a reversible capacity of 587.3 mAh/g at 0.2 A/g, a discharge capacity as high as 511.3 mAh/g at a high rate of 50 A/g, and still maintains a capacity of 471.9 mAh/g even after 5000 cycles based on the mass of Se@MXene/Cu. With such excellent electrochemical kinetic properties, this study highlights the importance of designing various MXene-based composites with synergistic effects of 2D confined structure and Cu catalytic center for the development of high-performance alkali metal-chalcogen battery systems.

Iron nanoparticles surface decorated MXene via molten salts etching as selenium host for ultrafast sodium ion storage.

Sodium-selenium (Na-Se) batteries have gained attention due to their high energy density and power density, resulting from the liquid-liquid reaction at the interface in the dimethoxyethane electrolyte. Nevertheless, the pronounced shuttle effect of polyselenides causes low coulomb efficiency and inadequate cycling stability for Na-Se batteries. Herein, the iron nanoparticles surface modified accordion-like Ti3C2Tx MXene (MXene/Fe) synthesized via the molten salt etching is utilized as the host of Se species for high-performance Na-Se battery cathode. Benefiting from the layered structure and chemical adsorption of accordion-like MXene, the shuttle effect of the cathode is effectively inhibited. Simultaneously, electrochemical kinetics is boosted due to the catalytic effect of Fe nanoparticles, which facilitate the transformation of polyselenide from long-chain to short-chain, contributing to pseudocapacitive capacity. Consequently, the Se-based cathode delivers a steady capacity of 575.0 mA h g-1 at 0.2 A/g, and even a high capacity of 500 mAh/g at 50 A/g based on the mass of Se@MXene/Fe electrode, indicating the ultrafast Na+ ion storage. Most notably, this structure demonstrated remarkable long-term cycling stability for 5000 cycles with a high capacity retention of 97.4 %. The electrochemical energy storage mechanism is further revealed by in situ Raman. Herein, the confinement-catalysis structure shines light on inhibiting shuttling and facilitating ultrafast ion storage.

A dual heterostructure enables the stabilization of 1T-rich MoSe2 for enhanced storage of sodium ions.

Electron injection effectively induces the formation of a 1T-rich phase to address the low conductivity of MoSe2. Nevertheless, overcoming the inherent metastability of the 1T phase (particularly during the conversion reactions that entail the decomposition-reconstruction of MoSe2 and volume expansion) remains a challenge. Guided by DFT results, we designed a composite with bimetal selenides-based heterostructures anchored on reduced graphene oxide (rGO) nanosheets (G-Cu2Se@MoSe2) to obtain stabilized 1T-rich MoSe2 and enhanced ion transfer. The construction of 1T-rich MoSe2 and built-in electric fields (BiEF) through electron transfer at the heterointerfaces were realized. Moreover, the rGO-metal selenides heterostructures with in situ-formed interfacial bonds could facilitate the reconstruction of the 1T-rich MoSe2-involved heterostructure and interfacial BiEF. Such a dual heterostructure endowed G-Cu2Se@MoSe2 with an excellent rate capability with a capacity of 288 mA h g-1 at 50 A g-1 and superior cycling stability with a capacity retention ratio of 89.6% (291 mA h g-1) after 15 000 cycles at 10 A g-1. Insights into the functional mechanism and structural evolution of the 1T MoSe2-involved dual heterostructure from this work may provide guidelines for the development of MoSe2 and phase-engineering strategies for other polymorphistic materials.

MoP quantum dots based multifunctional efficient electrocatalyst for stable and long-life flexible lithium-sulfur batteries.

The commercialization of lithium-sulfur (Li-S) batteries is challenging, owing to factors like the poor conductivity of S, the 'shuttle effect', and the slow reaction kinetics. To address these challenges, MoP quantum dots were decorated on hollow carbon spheres (MoPQDs/C) in this study and used as an efficient lithium polysulfides (LiPSs) adsorbents and catalysts. In this approach polysulfides are effectively trapped through strong chemisorption and physical adsorption while simultaneously facilitating LiPSs conversion by enhancing the reaction kinetics. MXene serves as a flexible physical barrier (MoPQDs/C@MXene), further enhancing the confinement of LiPSs. Moreover, both materials are conductive, significantly facilitating electron and charge transfer. Additionally, the flexible MoPQDs/C@MXene-S electrode offers a large specific surface area for sulfur loading and withstand volume expansion during electrochemical processes. As a result, the MoPQDs/C@MXene-S electrode exhibits excellent long-term cyclability and maintains a robust specific capacity of 992 mA h g-1 even after 800cycles at a rate of 1.0C (1C = 1675 mA g-1), with a minimal capacity decay rate of 0.034 % per cycle. This work proposes an efficient strategy to fabricate highly efficient electrocatalysts for advanced Li-S batteries.

Effects of exogenous thermophilic bacteria and ripening agent on greenhouse gas emissions, enzyme activity and microbial community during straw composting.

This research examined the impact of exogenous thermophilic bacteria and ripening agents on greenhouse gas (GHG) emission, enzyme activity, and microbial community during composting. The use of ripening agents alone resulted in a 30.9 % reduction in CO2 emissions, while the use of ripening agents and thermophilic bacteria resulted in a 50.8 % reduction in N2O emissions. Pearson's analysis showed that organic matter and nitrate nitrogen were the key parameters affecting GHG emissions. There was an inverse correlation between CO2 and CH4 releases and methane monooxygenase α subunit and N2O reductase activity (P<0.05). Additionally, N2O emissions were positively related to ß-1, 4-N-acetylglucosaminidase, and ammonia monooxygenase activity (P<0.05). Deinococcota, Chloroflexi, and Bacteroidota are closely related to CO2 and N2O emissions. Overall, adding thermophilic bacteria represents an effective strategy to mitigate GHG emissions during composting.

Anomalous water molecular gating from atomic-scale graphene capillaries for precise and ultrafast molecular sieving.

The pressing crisis of clean water shortage requires membranes to possess effective ion sieving as well as fast water flux. However, effective ion sieving demands reduction of pore size, which inevitably hinders water flux in hydrophilic membranes, posing a major challenge for efficient water/ion separation. Herein, we introduce anomalous water molecular gating based on nanofiltration membranes full of graphene capillaries at 6 Å, which were fabricated from spontaneous π-π restacking of island-on-nanosheet graphitic microstructures. We found that the membrane can provide effective ion sieving by suppressing osmosis-driven ion diffusion to negligible levels (~10-4 mol m-2 h-1); unexpectedly, ultrafast bulk flow of water (45.4 L m-2 h-1) was still functional with ease, as gated on/off by adjusting hydrostatic pressures within only 10-2 bar. We attribute this seemingly incompatible observation to graphene nanoconfinement effect, where crystal-like water confined within the capillaries hinders diffusion under osmosis but facilitates high-speed, diffusion-free water transport in the way analogous to Newton's cradle-like Grotthus conduction. This strategy establishes a type of liquid-solid-liquid, phase-changing molecular transport for precise and ultrafast molecular sieving.

Application of Inorganic Quantum Dots in Advanced Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have emerged as one of the most attractive alternatives for post-lithium-ion battery energy storage systems, owing to their ultrahigh theoretical energy density. However, the large-scale application of Li-S batteries remains enormously problematic because of the poor cycling life and safety problems, induced by the low conductivity , severe shuttling effect, poor reaction kinetics, and lithium dendrite formation. In recent studies, catalytic techniques are reported to promote the commercial application of Li-S batteries. Compared with the conventional catalytic sites on host materials, quantum dots (QDs) with ultrafine particle size (<10 nm) can provide large accessible surface area and strong polarity to restrict the shuttling effect, excellent catalytic effect to enhance the kinetics of redox reactions, as well as abundant lithiophilic nucleation sites to regulate Li deposition. In this review, the intrinsic hurdles of S conversion and Li stripping/plating reactions are first summarized. More importantly, a comprehensive overview is provided of inorganic QDs, in improving the efficiency and stability of Li-S batteries, with the strategies including composition optimization, defect and morphological engineering, design of heterostructures, and so forth. Finally, the prospects and challenges of QDs in Li-S batteries are discussed.