Dual-Component Interlayer Enables Uniform Lithium Deposition and Dendrite Suppression for Solid-State Batteries.

ß-Lithium thiophosphate (LPS) exhibits high Li+ conductivity and has been identified as a promising ceramic electrolyte for safe and high-energy-density all-solid-state batteries. Integrating LPS into solid-state lithium (Li) batteries would enable the use of a Li electrode with the highest deliverable capacity. However, LPS-based batteries operate at a limited current density before short-circuiting, posing a major challenge for the development of application-relevant batteries. In this work, we designed a dual-component interfacial protective layer called LiSn-LiN that forms in situ between the Li electrode and LPS electrolyte. The LiSn component, Li22Sn5, exhibits enhanced Li diffusivity compared with the metallic lithium and facilitates a more uniform lithium deposition across the electrode surface, thus eliminating Li dendrite formation. Meanwhile, the LiN component, Li3N, shows enhanced mechanical stiffness compared with LPS and functions to suppress dendrite penetration. This chemically robust LiSn-LiN interlayer provides a more than doubled deliverable critical current density compared to systems without interfacial protection. Through combined XPS and XAFS analyses, we determined the local structure and the formation kinetics of the key functional Li22Sn5 phase formed via the electrochemical reduction of a Sn3N4 precursor. This work demonstrates an example of the structural-specific design of a protective interlayer with a desired function - dendrite suppression. The structure of a functional protective layer for a given solid-state battery should be tailored based on the given battery configuration and its unique interfacial chemistry.

Cellulose-Encapsulated Composite Electrolyte Design: Toward Chemically and Mechanically Enhanced Solid-Sodium Batteries.

Sulfide- and halide-based ceramic ionic conductors exhibit comparable ionic conductivity with liquid electrolytes and are candidates for high-energy- and high-power-density all-solid-state batteries. These materials, however, are inherently brittle, making them unfavorable for applications. Here, we report a mechanically enhanced composite Na+ conductor that contains 92.5 wt % of sodium thioantimonate (Na3SbS4, NSS) and 7.5 wt % of sodium carboxymethyl cellulose (CMC); the latter serves as the binder and an electrochemically inert encapsulation layer. The ceramic and binder constituents were integrated at the particle level, providing ceramic NSS-level Na+ conductivity in the NSS-CMC composite. The more than 5-fold decrease of electrolyte thickness obtained in NSS-CMC composite provided a 5-fold increase in Na+ conductance compared to NSS ceramic pellets. As a result of the CMC encapsulation, this NSS-CMC composite shows increased moisture resistivity and electrochemical stability, which significantly promotes the cycling performance of NSS-based solid-state batteries. This work demonstrates a well-controlled, orthogonal process of ceramic-rich, composite electrolyte processing: independent streams for ceramic particle formation along with binder encapsulation in a solvent-assisted environment. This work also provides insights into the interplay among the solvent, the polymeric binder, and the ceramic particles in composite electrolyte synthesis and implies the critical importance of identifying the appropriate solvent/binder system for precise control of this complicated process.

Pore characteristics of sulfate-activated coal gasification slag cement paste backfill for mining.

With the mass production of coal-based solid waste, coal mine filling can effectively consume it. The coal gasification slag is modified and prepared as coal mine filling material to meet the relevant technical requirements, which can realize the recycling of coal mine → coal chemical industry → coal mine. In this paper, in order to explore the evolution law of the mechanical properties and pore structure characteristics of the modified coal gasification slag-cement cemented paste backfill (MCGS-CPB) prepared by sodium sulfate excitation coal gasification slag, a combined macro-meso-micro testing method is used. MCGS-CPB with different sodium sulfate contents (1~5%) were prepared and tested for uniaxial compressive strength (UCS), mercury intrusion (MIP) and microscopic tests. The results show that sodium sulfate has a significant effect on the UCS and pore structure characteristics of MCGS-CPB. The mechanical properties and pore structure characteristics of MCGS-CPB were best when sodium sulfate was doped at 3%; the mechanical properties and pore structure characteristics of MCGS-CPB were deteriorated when the addition of sodium sulfate is higher than 3%. On the meso-scale, when sodium sulfate was doped with 3%, the more harmful pores of MCGS-CPB gradually changed into harmless, less harmful, and harmful pores, and the macroscopic mechanical properties were gradually improved; when the addition of sodium sulfate is higher than 3%, the harmless, less harmful, and harmful pores of MCGS-CPB gradually changed into more harmful pores, and the macroscopic mechanical properties were deteriorated. On a microscopic scale, sodium sulfate can cause MCGS-CPB to form hydration products with expansion properties. The presence of a reasonable amount of sodium sulfate in the pores of MCGS-CPB is beneficial to the development of mechanical properties. However, excessive presence will lead to the formation of expansion stress, gradual formation of micro-expansion cracks, and deteriorate the macroscopic mechanical properties. Hence, the volcanic ash activity of coal gasification slag excited by external addition of sodium sulfate should not exceed 3%. This study provides a reference value for application ratio of sodium sulfate-stimulated MCGS-CPB used in coal mine filling design.

Mechanochemistry in Sodium Thioantimonate Solid Electrolytes: Effects on Structure, Morphology, and Electrochemical Performance.

Sodium thioantimonate (Na3SbS4) and its W-substituted analogue Na2.88Sb0.88W0.12S4 have been identified as potential electrolyte materials for all-solid-state sodium batteries due to their high Na+ conductivity. Ball milling mechanochemistry is a frequently employed synthetic approach to produce such Na+-conductive solid solutions; however, changes in the structure and morphology introduced in these systems via the mechanochemistry process are poorly understood. Herein, we combined X-ray absorption fine structure spectroscopy, Raman spectroscopy, solid-state nuclear magnetic resonance spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy characterization techniques to provide an in-depth analysis of these solid electrolytes. We report unique changes seen in the structure and morphology of Na3SbS4 and Na2.88Sb0.88W0.12S4 resulting from ball milling, inducing changes in the electrochemical performance of the solid-state batteries. Specifically, we observed a tetragonal-to-cubic crystal phase transition within Na3SbS4 following the ball mill, resulting in an increase in Na+ conductivity. In contrast, the Na+ conductivity was reduced in mechanochemically treated Na2.88Sb0.88W0.12S4 due to the formation and accumulation of a WS2 phase. In addition, mechanochemical treatment alters the surface morphology of densified Na2.88Sb0.88W0.12S4 pellets, providing intimate contact at the solid electrolyte/Na interface. This phenomenon was not observed in Na3SbS4. This work reveals the structural and morphological origin of the changes seen in these materials' electrochemical performance and how mechanochemical synthesis can introduce them.

Investigating the synergistic effects of magnesia-coal slag based solid waste cementitious materials and its basic characteristics as a backfill material.

Applying solid waste resources as backfill material can reduce both the cost of backfill and the environmental problems caused by solid waste landfills. In this paper, the synergistic reaction effects of solid waste modified magnesia slag (MMS), coal gasification slag (CGS), and desulfurized gypsum (DG) as magnesium-coal slag based cementitious materials (MCC) and their preliminary feasibility as mining cementitious materials in synergy with coal gangue for the preparation of backfill materials are investigated. The results show that the order of the compressive strength of the cementitious systems is ternary system > binary system > monolithic system, which proves the existence of synergistic effect among MMS, CGS, and DG and determines the optimal dosing of each raw material in the ternary system. At early ages, the physical effect of CGS and the chemical effect of DG in the ternary system can promote the hydration reaction of MMS, but the synergistic effect between the three is weak; At later ages, a synergistic effect occurred among silica-aluminate depolymerization in CGS, dissolved sulfate from DG and hydration products from MMS, which promoted the production of more hydration products calcium-silicate(aluminum)-hydrate (C-S(A)-H) and AFt, and improved the compressive strength. In addition, the strength, fluidity and leaching of the backfill material prepared by MCC in collaboration with coal gangue can meet the preliminary feasibility for mine backfill. In the present work, the full solid waste MCC is developed to completely replace cement and use it to prepare backfill materials, which is of great importance to the comprehensive utilization of bulk solid waste, the reduction of backfill costs, and the enhancement of the economic and ecological interests of mines.

Basic characteristics of magnesium-coal slag solid waste backfill material: Part I. preliminary study on flow, mechanics, hydration and leaching characteristics.

The environmental damage caused by surface subsidence and coal-based solid waste (CBSW) is a common problem in the process of coal mining. Backfill mining can control the mining-induced subsidence and solve the problem of bulk solid waste storage. In the present work, a magnesium-coal slag solid waste backfill material (MCB) with modified magnesium slag (MS) as binder and CBSW (fly ash (FA), flue gas desulfurization gypsum (FDG) and coal gasification slag (CGS)) as supplementary cementitious material/aggregate was proposed to meet the needs of coal mining in Northern Shaanxi, China, to realize the comprehensive treatment of goaf and CBSW. The results show that: (1) The rheological curve of the fresh MCB slurry is highly consistent with the Herschel-Bulkley (H-B) model, and its fluidity meets the basic requirements of mine backfill pumping. With the addition of FDG and MS, the yield stress, apparent viscosity and thixotropy of MCB slurry increase, while the pseudoplastic index and slump decrease. (2) The strength of MCB develops slowly in the early stage (0∼14 days) and increases rapidly in the later stage (14∼90 days). Except for the ratio of M20F1 and FDG = 0%, the strength of samples at other ratios (at 28 days) is between 6.06∼11.68 MPa, which meets the strength requirement of 6 MPa for coal mine backfill. The addition of MS and appropriate amount of FDG is beneficial to the development of strength. In contrast, MS exhibits a significant improvement in early strength, and FDG has a significant improvement in late-age strength. (3) Corresponding to the compressive strength, the hydration products C-S(A)-H and AFt of MCB are less in the early stage and greatly increased in the later stage. The active substance in FA/CGS will undergo pozzolanic reaction with the MS hydration product CH. The addition of FDG and MS can promote the reaction and increase the amount of hydration product, but in contrast, the promotion effect of FDG is more significant. (4) The amount of heavy metal leaching of MCB meets the requirements of national standards. The hardened MCB has a solidification/stabilization effect on heavy metal elements, which can significantly reduce the amount of heavy metal leaching. The results imply that MCB is a safe, reliable, and eco-friendly solid waste backfill material, and its application is conducive to the coordinated development of coal resource mining and environmental protection.

Degradation at the Na3SbS4/Anode Interface in an Operating All-Solid-State Sodium Battery.

All-solid-state sodium batteries utilize earth-abundant elements and are sustainable systems for large-scale energy storage and electric transportation. Replacing flammable carbonate-based electrolytes with solid-state ionic conductors promotes battery safety. Using solid-state electrolytes (SEs) also eliminates the need for packing when fabricating tandem cells, potentially enabling further enhanced energy density. Na3SbS4, a Na+ conductor, remains stable in dry air and shows high Na+ conductivity (σ ≈ 1.0 × 10-3 S/cm) and is thus a promising SE for applications in sodium batteries. However, upon repeated electrochemical cycling, Na3SbS4-containing Na batteries exhibit decaying capacity and limited cycle life, which is likely associated with the decomposition of Na3SbS4 at the electrode/electrolyte interface. This work presents an in-depth analysis of the decomposition chemistry occurring at the Na3SbS4/anode interface using combined in situ Raman and post-mortem characterization. The results indicate that the SbS43- counterion is electrochemically reduced when experiencing Na+ reduction potentials, and this reduction chemistry likely follows multiple pathways. The observed reduction products include SbS33-, the Sb2S74- dimer, the NaSb binary phase, and Na2S. We also observed the irreversibility of the decomposition and, as a consequence, the accumulation of the degradation products over cycles. Also notable is the heterogeneity of this degradation chemistry across the interface. Through the spectroelectrochemical characterizations, we reveal the possible mechanisms of the Na3SbS4 decomposition at the solid electrolyte/anode interface in an operating device.

Influence of Mechanical Grinding on Particle Characteristics of Coal Gasification Slag.

Based on the test results of laser particle size analyzer, specific surface area analyzer and infrared spectrometer, the grinding kinetics of coal gasification slag (CGS) was systematically described by using Divas-Aliavden grinding kinetics, Rosin-Rammler-Bennet (RRB) distribution model and particle size fractal theory. The influence of grinding time and particle group of CGS on the strength activity index of mortar was studied by using the strength activity index of mortar and grey correlation analysis. The results show that the particles are gradually refined before mechanical grinding of CGS for 75 min. When the mechanical grinding time is greater than 75 min, the "agglomeration phenomenon" of fine CGS particles led to the decrease in various properties. Divas-Aliavden grinding kinetics, the RRB model and fractal dimension can characterize the change of CGS particle size in the grinding process quantitatively. The strength activity index of CGS at different curing ages is positively correlated with grinding time, and the influence on the later strength activity index is the most obvious. The relationship between CGS particle size distribution and strength activity index were probed using grey correlation analysis. The CGS particle groups with the particle size of 20~30 µm and 10~20 µm have the greatest impact on the early and late strength activity index, respectively. Therefore, the optimal grinding time of CGS as auxiliary cementing material is 75 min, considering factors, such as economy and performance, and the specific surface area (SSA) is 4.4874 m2·g-1.

Modeling Notch-Induced Tumor Cell Survival in the Drosophila Ovary Identifies Cellular and Transcriptional Response to Nuclear NICD Accumulation.

Notch is a conserved developmental signaling pathway that is dysregulated in many cancer types, most often through constitutive activation. Tumor cells with nuclear accumulation of the active Notch receptor, NICD, generally exhibit enhanced survival while patients experience poorer outcomes. To understand the impact of NICD accumulation during tumorigenesis, we developed a tumor model using the Drosophila ovarian follicular epithelium. Using this system we demonstrated that NICD accumulation contributed to larger tumor growth, reduced apoptosis, increased nuclear size, and fewer incidents of DNA damage without altering ploidy. Using bulk RNA sequencing we identified key genes involved in both a pre- and post- tumor response to NICD accumulation. Among these are genes involved in regulating double-strand break repair, chromosome organization, metabolism, like raptor, which we experimentally validated contributes to early Notch-induced tumor growth. Finally, using single-cell RNA sequencing we identified follicle cell-specific targets in NICD-overexpressing cells which contribute to DNA repair and negative regulation of apoptosis. This valuable tumor model for nuclear NICD accumulation in adult Drosophila follicle cells has allowed us to better understand the specific contribution of nuclear NICD accumulation to cell survival in tumorigenesis and tumor progression.

Use of iron oxide nanomaterials in wastewater treatment: a review.

Nowadays there is a continuously increasing worldwide concern for the development of wastewater treatment technologies. The utilization of iron oxide nanomaterials has received much attention due to their unique properties, such as extremely small size, high surface-area-to-volume ratio, surface modifiability, excellent magnetic properties and great biocompatibility. A range of environmental clean-up technologies have been proposed in wastewater treatment which applied iron oxide nanomaterials as nanosorbents and photocatalysts. Moreover, iron oxide based immobilization technology for enhanced removal efficiency tends to be an innovative research point. This review outlined the latest applications of iron oxide nanomaterials in wastewater treatment, and gaps which limited their large-scale field applications. The outlook for potential applications and further challenges, as well as the likely fate of nanomaterials discharged to the environment were discussed.

Oxalate production at different initial Pb²+ concentrations and the influence of oxalate during solid-state fermentation of straw with Phanerochaete chrysosporium.

The production of oxalate at different initial Pb(2+) concentrations during solid-state fermentation of straw with Phanerochaete chrysosporium was investigated. It was found that the maximal peak value of oxalate concentration (22.84 mM) was detected at the initial Pb(2+) concentration of 200 mg kg(-1) dry straw, while the minimum (15.89 mM) at the concentration of 600 mg Pb(2+)kg(-1) dry straw, and at moderate concentration of Pb(2+) the capability of oxalic acid secretion was enhanced. In addition, it was also found that more oxalic acid accumulation went together with better Pb(2+) passivation effect and higher manganese peroxidase (MnP) activity. The present findings will improve the understandings of the interactions of heavy metals with white-rot fungi and the role of oxalate in lignin degradation system, which could provide useful references for more efficient treatment of Pb-contaminated lignocellulosic waste.

[Performance of desulfurizing absorbent of roasted navajoite].

An innovative flue gas desulfurization (FGD) coupling process was proposed in this study to overcome the problems in wet-type limestone/lime processes which include fouling, clogging, and difficulty of selling the by-products and the problems in traditional process for vanadium extraction from navajoite ore such as excessive consumption of sulfuric acid and emissions of pollutants. The performance of a jet bubbling reactor (JBR) at pilot-scale was evaluated using navajoite ore produced in the process of extracting vanadium pentoxide as desulfurization absorbent. Results showed that navajoite ore slurry achieved better desulfurization performance than limestone slurry. When the inlet flue gas pressure drop was 3.0 kPa, the gas flow was about 2350 m3 x h(-1) and the pH of the navajoite ore slurry was higher than 4.5, the desulfurization efficiency was stable about 90%. The SO2 removal efficiency appeared to increase along with the increasing of absorbent cycle-index. The efficiency of the second circulation was improved 3.5% compared to the first circulation. After an operating duration of 40 minutes, the leaching rate of vanadium pentoxide was about 20%, and reached 60% when the by-products were leached with 5% dilute sulfuric acid for 10 hours. The by-product from this process not only could be used to produce vanadium pentoxide which is a valuable industrial product, but also could significantly overcome the pollution problem existing in the traditional refining process of vanadium pentoxide when navajoite ore is used as the feed material. This FGD process using roasted navajoite slurry as absorbent is environmental sound and cost-effective, and shows the potential for application in the field of flue gas desulfurization as well as hydrometallurgy.

[Research and application of producing laccase by Phanerochaete chrysosporium in solid-state fermentation system].

The potential of banana skin and corn cob as a support-substrate for the production of extracellular laccase by the white-rot fungus Phanerochaete chrysosporium (BKMF-1767) was investigated. The results indicate that laccase showed a maximum activity of 12.68 U/g when the proportion of banana skin and corn cob is 1:2 and the inducer is 0.4 mmol/L CuSO4. In addition, crude laccase enzyme shows degradation activity to pentachlorophenol (PCP) without redox mediator or with the redox mediator (ABTS) at a concentration of 5 mmol/L, and the degradation rates of PCP were 37.8% and 97% respectively after 6 h. The crude laccase was purified by treatment of (NH4)2SO4, and the purified laccase could make the degradation rate of PCP to 81.8% within 6 h.

[Optimization of piggery wastewater treatment with combined anaerobic hydrolysis and SBR process].

Anaerobic sequence batch reactor and aerobic sequence batch reactor were combined to treat the piggery wastewater. The ASBR was used to digest the wastewater for primary organic matter removal. Infections of digestion time to the wastewater's BOD/COD and to the nitrogen removal in behind SBR were studied. The result indicated that the wastewater with 36 hours' digestion retained high BOD/COD ratio of about 0.4. The nitrogen removal efficiency of this kind of wastewater in behind SBR was high with the effluent NH4+-N concentration less than 10 mg/L and a removal ratio higher than 99%. The total BOD5 removal ratio of A/O SBR was higher than 98% but the effluent COD(Cr) concentration couldn't meet the discharging standard before coagulating sedimentation.