Cycling Processes Research Articles

Carbon-encapsulated silicon ordered nanofiber membranes as high-performance anode material for lithium-ion batteries

Silicon have attracted much attention as a promising anode material for lithium-ion batteries due to the extremely high theoretical capacity. However, its practical application is limited by the huge volume expansion during the cycling process. To address this issue, carbon-encapsulated silicon ordered nanofiber membranes were designed through a modified electrospinning technology with a strong magnetic field. Compared with the conventional nanofiber membranes, the optimized M1200 Gs anode exhibited a high discharge capacity of 1603.1 mAh·g−1 at 0.1 A·g−1, a superior rate performance, and a robust cycling stability with a reversible capacity of 658.1 mAh·g−1 at 1 A·g−1 after 100 cycles. The improved electrochemical performance was confirmed to be highly correlated with the parallel structure of nanofibers, which help to facilitate the diffusion and transport of electrons and ions, realize the stress distribution and buffer the volume changes. This work provides unique insights into designing silicon-based anodes with novel structures for lithium-ion batteries.

Influence of soil organic carbon fractions on the soil priming effect under different vegetation restoration modes

AbstractThe soil priming effect is a key mechanism influencing carbon (C) cycling processes between the forest soil organic carbon (SOC) pool and the atmosphere. Different vegetation restoration modes have different SOC pool compositions, and it is not clear whether such differences affect the soil priming effect. Therefore, we selected soil from six typical vegetation restoration modes Platycladus orientalis (PO), Pinus sylvestris (PS), Quercus acutissima (QA), shrub (SH) and wasteland (WL) in the soil and rocky mountainous areas of northern China and measured the soil properties, microbial communities, microbial necromass carbon (MNC), SOC fractions and the soil priming effect. The SOC content decreased in the order of PO (21.33 g kg−1), PS (22.00 g kg−1), QA (13.67 g kg−1), SH (13.33 g kg−1) and WL (10.33 g kg−1), and the trends of the mineral‐associated organic carbon (MAOC) and fungal necromass carbon (FNC) content were the same as those of the SOC content. The soil priming effect was greater in both forests and shrublands than in wastelands, with the greatest effect occurring in PO forests, where the soil priming effect reached 159.91 mg CO2‐C kg−1 soil after 30 days of incubation, which was 1.4 times greater than that in WL. The soil priming effect was mainly determined by the difference in MAOC content. In addition, the soil C/N ratio and bacterial community diversity also indirectly affected the soil priming effect by influencing the soil MNC and SOC fractions. Overall, afforestation increased the SOC content, fungal necromass contribution and mineral conservation, increasing the soil priming effect. This theoretical foundation supports the enhancement of SOC sequestration capacity by implementing various modes of vegetation restoration in the future.

Inducing One-Step Dehydrogenation of Magnesium Borohydride via Confinement in Robust Dodecahedral Nitrogen-Doped Porous Carbon Scaffold.

A dodecahedral activated N-doped porous carbon scaffold is synthesized and used for the nanoconfinement of Mg(BH4)2. The optimized mesoporous scaffold possesses an accumulated pore width of 2.65nm, high specific surface area (3955.9 m2g-1), and large pore volume (2.15 cm3g-1), providing ample space for the confinement of Mg(BH4)2 particles and numerous surface active sites for interactions with the same. The confined Mg(BH4)2 system features a dehydrogenation onset temperature of 81.5°C, an extremely high capacity of 10.2 wt% H2, and an almost single-step dehydrogenation profile. Moreover, the system exhibits superior capacity retention of 82.7% after 20 cycles at a moderate temperature of 250°C. Precise activation control enables a transformation from microporous carbon materials to mesoporous ones, and hence the efficient nanoconfinement of Mg(BH4)2 and realization of one-step dehydrogenation. The evolution of borohydride intermediates is systematically revealed throughout the cycling process. Density functional theory calculations demonstrate defective N heteroatoms within the scaffold are vital in reducing the strength of B─H bonds, and the N-doped carbon can facilitate decomposition of the irreversible MgB12H12 intermediate. This study opens up new avenues for designing robust carbon scaffolds doped with heteroatoms and analyzing intermediate evolution in nanoconfined Mg-based borohydride systems.

Facile synthesis of GexSiO(1-x) alloys as a superior anode enables high-energy lithium-ion batteries

The large-scale development of low-cost silicon monoxide (SiO) anode is limited due to its low initial Coulombic efficiency (ICE) and poor cycle stability. Herein, the GexSiO(1-x) (0<x<1) composite anode has been facile synthesized by introducing germanium (Ge) atoms disrupted the structure of SiO matrix, which exhibits superior lithium storage performance. In particular, the optimized Ge0.5SiO0.5 electrode with nanoscale dispersion shows a high ICE of 80.2 % and a reversible capacity of 673.9 mAh g−1 after 100 cycles. To evaluate the effect of the Ge addition on the electrochemical properties, the lithium storage behaviors and structural evolution of the GexSiO(1-x) electrodes are investigated systematically. The in-situ electrochemical dilatometry reveals that the Ge0.5SiO0.5 electrode displays a better reversible thickness variation during cycling process. Density functional theory (DFT) calculation demonstrates that the SiGe domain can accommodate the volume expansion of Si and Ge domains. Moreover, the relationships between the electrochemical performance and morphology evolution demonstrate that the disordered structure and nanoscale distribution of Ge0.5SiO0.5 electrodes are the main reasons for improving ICE and cycle stability. This work provides a commercially available synthetic route for the design of advanced anode materials for large-scale energy storage applications.

Enhanced denitrification by sunlight–hematite: A neglected nitrogen flow pattern in red soil

Mineral-microbe interactions in the Earth's Critical Zone significantly influence elemental biogeochemical cycling and energy flow processes. This study addresses the key scientific question of how semiconducting minerals drive microbial nitrogen cycling. In the red soil environment, the presence of semiconducting minerals enhances the denitrification process mediated by facultative microorganisms (Pseudomonas aeruginosa PAO1) with denitrifying activity. Compared to darkness, light significantly enhanced the synergistic denitrification kinetic process of red soil and Pseudomonas aeruginosa PAO1 (1.87 times). Cyclic voltammetry shows that the P. aeruginosa PAO1-red soil synergistic system exhibits distinct redox peaks under light. The constant potential current curve and electrochemical impedance spectroscopy measurements reveal a high photocurrent density (1.0 μA/cm2) and minimal polarization resistance (102 Ω) under this condition. These findings confirm that the sunlight-red soil-P. aeruginosa PAO1 synergistic process has excellent electron generation and migration capacity, active redox reactions, and good electron compatibility. Additionally, the photoelectrons of semiconductive minerals in red soil profoundly impact the metabolic processes of microbial denitrification functional genes. Using real-time polymerase chain reaction (qPCR) gene array technology, the abundance of nitrogen metabolism functional genes in P. aeruginosa PAO1 increased by 200 % during the light-red soil synergistic process. Notably, denitrification-related genes (ureC, nirS1, gdhA, and nosZ2) were significantly upregulated. This study confirms that semiconducting minerals are involved in the nitrogen cycle pathway of microbial denitrification and supplements the theory of mineral-microbial synergistic element biogeochemical cycling in the natural environment.

Nutrient Addition Enhances the Temperature Sensitivity of Soil Carbon Decomposition Across Forest Ecosystems.

Atmospheric nitrogen (N) and phosphorus (P) depositions have been shown to alter nutrient availability in terrestrial ecosystems and thus largely influence soil carbon cycling processes. However, the general pattern of nutrient-induced changes in the temperature response of soil carbon decomposition is unknown. Yet, understanding this pattern is crucial in terms of its effect on soil carbon-climate feedback. Here, we report that N and P additions significantly increase the temperature sensitivity of soil organic carbon decomposition (Q10) by sampling soils from 36 sites across China's forests. We found that N, P, and their co-addition (NP) significantly increased the Q10 by 11.3%, 11.5%, and 23.9%, respectively. The enhancement effect of nutrient addition on Q10 was more evident in soils from warm regions than in those from cold regions. Moreover, we found that nutrient-induced changes in substrate availability and initial substrate and nutrient availability mainly regulated nutrient addition effects. Our findings highlight that N and P deposition enhances the temperature response of soil carbon decomposition, suggesting that N and P deposition should be incorporated into Earth system models to improve the projections of soil carbon feedback to climate change.

Effects of Nitrogen Forms on Soil Enzyme Activities in a Saline-Alkaline Grassland.

Global climate change and agricultural practices have increased atmospheric nitrogen (N) deposition, significantly affecting the nitrogen cycling process in grasslands. The impact of different N forms on key soil enzyme activities involved in N nitrification, particularly in the saline-alkali grasslands of the Hexi Corridor, using natural grassland as a control (CK) and adding three N treatments: inorganic N (IN), organic N (ON) and a mixed N treatment (MN, with a 4:6 ratio of organic to inorganic N). Our study assessed the effects of these N forms on soil properties and enzyme activities crucial for N cycling. The findings indicate that different N forms significantly enhance soil mineral N content, with ON treatment leading to the highest increases in nitrate and ammonium content 92.44% and 35.6%, respectively, compared to CK. Both IN and ON treatments significantly boosted soil nitrate reductase and urease activities (p < 0.05), while MN treatment decreased nitrate reductase activity, with ON treatment showing the greatest sensitivity to enzyme activity changes. Soil pH slightly increased with N addition, but soil nitrite reductase activity remained relatively unchanged (0.372-0.385 mg g-1). Correlation analysis revealed that soil mineral N content and pH are key regulators of enzyme activities in saline-alkaline grasslands. These results suggest that different N forms should be considered in nutrient cycling models, with organic N addition potentially enhancing soil N conversion and mitigating nutrient limitations in grassland ecosystems.

High-capacity and long-life Fe2O3/MOFs composite anodes: Preparation, characterization, morphology regulation and electrochemical performance

Among the various transition metal oxides used in lithium-ion battery anodes, iron oxide (Fe2O3) has received extensive attention due to its low cost, good environmental compatibility and high theoretical capacity. However, the volume expansion and structural collapse during the charging-discharging cycling process significantly limited the practical application of Fe2O3. Herein, we demonstrate enhanced electrochemical properties and stability of Fe2O3 by anchoring it on metal-organic frameworks (MOFs). Through adjusting the MOF ligands and introducing humic acid (HA), we reached rational control of the morphology for the Fe2O3/MOF composites. The optimized sample, namely Fe2O3@HA-Fe-ATA, shows 3D cauliflower-like structure with abundant pores, which are beneficial to the active sites exposure, electrolyte penetration, as well as the tolerance toward volume expansion. Consequently, high reversible capacity of 1442.7 mAh g−1 (at 0.1 A g−1), excellent rate performance (<11 % capacity decrease when current density increases from 0.1 A g−1 to 1 A g−1), and satisfactory cycle stability (91 % capacity retention after 500 cycles at 1 A g−1) are obtained. This work demonstrates that the rational design of MOF by introduction of appropriate ligand is a very efficient approach to optimize the electrochemical properties of the resultant electrode material.

Investigation of the microstructural characteristics of laser-cladded Ti6Al4V titanium alloy and its corrosion behavior in simulated body fluid

Laser cladding technology has a wide range of potential industrial applications in the surface strengthening, repair and reuse of orthopedic implants. By employing this technique to conduct same-material surface restoration and enhancement on titanium alloys, it demonstrates significant developmental potential. However, the microstructure of laser additively manufactured titanium alloy differs significantly from that of traditional titanium alloys, which affects its corrosion resistance in human body fluids. To compare the corrosion resistance differences between the cladding layer and the substrate, this study investigates the microstructure of multi-pass laser cladding Ti6Al4V (TC4) titanium alloy and analyzes the corrosion morphology and corrosion products of the cladding layer in simulated body fluids (SBF). By comparing the electrochemical corrosion behavior of laser cladding with that of traditionally manufactured TC4, this research reveals the differences in corrosion resistance between the two titanium alloys. The research demonstrates that the microstructure of cladding primarily consists of prior-β grains and continuous grain boundary α phase, along with a complex basketweave structure composed of fine acicular α phase and lamellar α phase. Additionally, due to the complex thermal cycling process, the acicular α' colonies within the prior-β grains. These features enhance the cladding layer’s resistance to plastic deformation and increase microhardness, though with some uneven distribution. Interestingly, the TC4 cladding layer forms a porous passivation layer after corrosion, primarily composed of a TiO2 passivation film and deposits of hydroxyapatite and other phosphates. Due to the lower β-phase content, finer grains with higher energy states, and a greater proportion of high-angle grain boundaries (HAGBs) in the cladding layer, it exhibits higher electrochemical activity. As a result of these microstructural differences, the corrosion resistance of the TC4 cladding layer in SBF is inferior to that of TC4 manufactured using traditional techniques.

Permeability evolution of sandstone caprock transverse fractures during intermittent CO2 injection in coal-bearing strata

The caprock of coal-bearing strata plays a critical role in CO2 geological storage, with the presence of fractures posing a heightened risk of CO2 leakage. The cyclic effects of CO2 injection and in situ stress influence the permeability of caprock fractures. However, the combined impact of CO2 and in situ stress on fracture permeability remains uncertain. This study conducted cyclic seepage experiments under varying amplitude stresses on fractured sandstone samples soaked in ScCO2 for different times (0, 15, 30, and 60 days). The microstructural characteristics of the fractured sandstone surfaces were analyzed using scanning electron microscopy and x-ray diffraction. The experimental results indicated that soaking in ScCO2 reduces sandstone fracture permeability, but the extent of this reduction is nonlinearly related to the soaking time. During the stress cycling process, due to the effect of plastic deformation, the permeability of sandstone fractures decreases with increasing cyclic amplitude and remains relatively constant with decreasing cyclic amplitude. At the same cyclic amplitude, the permeability of sandstone fractures initially increases and then decreases with prolonged soaking time. The impact of ScCO2 and stress cycling on the permeability of sandstone fractures is the result of a series of combined chemical–mechanical effects. The combined effects of chemical dissolution and mechanical degradation significantly influence the permeability of sandstone fractures, and this impact is notably time-dependent. During short-term soaking, geochemically induced changes in the surface structure of fractures cause fluctuations in permeability, while in long-term soaking, the combined chemical–mechanical effects promote a reduction in fracture permeability.

Altitudinal Variation in Soil Acid Phosphomonoesterase Activity in Subalpine Coniferous Forests in China

Studying the altitudinal variation and driving factors of soil acid phosphomonoesterase (ACP) activity in subalpine regions is crucial for understanding nutrient cycling processes within mountainous ecosystems. This study focused on fir (Abies fabri (Mast.) Craib) forests located at three altitudes (2781 m, 3044 m, and 3210 m) on the eastern slope of Mt. Gongga in southwest China. We measured soil ACP activity alongside soil climate, nutrients, and microorganisms at various depths and elevations to investigate how these factors influence ACP activity. The results indicated that in the organic matter horizons (Oe and Oa horizons), ACP activity gradually decreased with elevation. However, the surface mineral horizon (A horizon) did not show a decline in ACP activity with increasing elevation, which could be attributed to significantly lower ACP activity recorded at the 2781 m sample site compared to the 3044 m site. Variance partitioning analysis revealed that among soil climate, nutrients, and microorganisms, soil nutrients had the most substantial impact on ACP activity across all horizons, with a particularly high contribution of 89.4% observed in the A horizon. Random forest model analysis further demonstrated that soil total carbon (TC) played a crucial role in determining ACP activity in the Oe and Oa horizons, with importance values of 8.5% and 7.3%, respectively. Additionally, soil total nitrogen (TN) was identified as the primary factor influencing ACP activity in the A horizon, with an importance value of 12.6%. Furthermore, soil ACP activity was positively regulated by the soil TC:TP and TN:TP ratios, indicating a stoichiometric control of ACP activity in the Abies fabri (Mast.) Craib forests on Mt. Gongga.

Spatial-temporal patterns of foliar and bulk soil 15N isotopic signatures across a heterogeneous landscape: Linkages to soil N status, nitrate leaching, and N2O fluxes

The natural abundance of plant and bulk soil 15N isotopic signatures provides valuable insights into the magnitude of nitrogen cycling and loss processes within terrestrial ecosystems. However, 15N isotopic signatures are highly variable in space due to natural and anthropogenic factors affecting N cycling processes and losses. To date, most studies on foliar and bulk soil 15N isotopic signatures have focused on N-limited forest ecosystems at relatively large spatial scales, while similar studies in N-enriched ecosystems at finer spatial scales are lacking. To address this gap and evaluate links between soil 15N isotopic signatures and ecosystem N cycling and loss processes (plant N uptake, N leaching, and gaseous loss), this study quantified foliar and bulk soil 15N isotopic signatures, soil physicochemical parameters, gaseous (N2O), and hydrological (NO3) N losses at 80 sites distributed across a heterogeneous landscape (∼5.8 km2). To account for the spatial-temporal heterogeneity, the measurements were performed in four campaigns (March, June, September 2022, and March 2023) at sites that considered different land uses, soil types, and topography. Results indicated that foliar and bulk soil 15N isotopic signatures were significantly (P < 0.05) more enriched in arable and grassland ecosystems than forests, suggesting a more open N cycle with significant N cycling and losses due to higher N inputs from fertilizers. Similar to soil inorganic N, N2O fluxes, and NO3 leaching rates, landscape-scale foliar and soil 15N isotopic signatures varied widely spatially, particularly at grassland and arable land (−3 to 9.0‰), with bivariate and multivariate analyses also showing significant relationships between landscape-scale soil 15N isotopic signatures and the aforementioned parameters (r2: 0.29 to 0.82). Based on these relationships, our findings suggested that foliar and bulk 15N isotopic signatures may capture fine-scale areas with persistently high and low environmental N losses (N2O fluxes and NO3 leaching) within a heterogeneous landscape.

Bidirectional pH Buffer Effect Facilitates High-Reversible Aqueous Zinc Ion Batteries.

Aqueous zinc ion batteries (AZIBs) stand out from the crowd of energy storage equipment for their superior energy density, enhanced safety features, and affordability. However, the notorious side reaction in the zinc anode and the dissolution of the cathode materials led to poor cycling stability has hindered their further development. Herein, ammonium salicylate (AS) is a bidirectional electrolyte additive to promote prolonged stable cycles in AZIBs. NH4 + and C6H4OHCOO- collaboratively stabilize the pH at the interface of the electrolyte/electrode and guide the homogeneous deposition of Zn2+ at the zinc anode. The higher adsorption energy of NH4 + compared to H2O on the Zn (002) crystal plane mitigates the side reactions on the anode surface. Moreover, NH4 + is similarly adsorbed on the cathode surface, maintaining the stability of the electrode. C6H4OHCOO- and Zn2+ are co-intercalation/deintercalation during the cycling process, contributing to the higher electrochemical performance of the full cell. As a result, with the presence of AS additive, the Zn//Zn symmetric cells achieved 700h of highly reversible cycling at 5mA cm-2. In addition, the assembled NH4V4O10(NVO)//Zn coin and pouch batteries achieved higher capacity and higher cycle lifetime, demonstrating the practicality of the AS electrolyte additive.

Transcriptomic and protein analysis of Trametes versicolor interacting with a Hypholoma fasciculare mycelium foraging in soil

The decomposition of large woody material is an important process in forest carbon cycling and nutrient release. Cord-forming saprotrophic basidiomycete fungi create non-resource limited mycelial networks between decomposing branches, logs and tree stumps on the forest floor where colonisation of new resources is often associated with the replacement of incumbent decay communities. To date, antagonism experiments have mostly placed competing fungi in direct contact, while in nature cord-forming saprobes encounter colonised wood as mycelia in a network. Transcriptomic and peptide analyses were conducted on soil-based microcosms were foraging cord-forming Hypholoma fasciculare encountered a wood block colonised by Trametes versicolor. Protein turnover featured strongly for both species and genes putatively involved in secondary metabolite production were identified. H. fasciculare demonstrated an exploitative profile with increased transcription of genes associated with carbohydrate metabolism and RNA and ribosome processing. T. versicolor showed a shift in signalling, energy generation and amino acid metabolism. By identifying genes and proteins putatively involved in this fungal interaction, this work may help guide the discovery of bioactive molecules and mechanisms underpinning community succession.

Ca/Li Synergetic-Doped Na0.67Ni0.33Mn0.67O2 to Realize P2-O2 Phase Transition Suppression for High-Performance Sodium-Ion Batteries.

P2-type layered transition metal oxide Na0.67Ni0.33Mn0.67O2 is considered as a promising cathode for advanced sodium-ion batteries due to its high theoretical specific capacity. However, the P2-type cathode suffers severe P2-O2 phase transition during cycling process, resulting unsatisfactory cyclic stability and rate capability. Herein, a Ca/Li co-doped P2-type Na0.62Ca0.05Ni0.33Mn0.57Li0.10O2 (NCNMLO) cathode material was synthesized through a simple sol-gel method. With the synergistic effect of Ca-doping at Na sites and Li substitution at transition metal (TM) sites, the cathode achieves an excellent electrochemical performance due to the inhibited P2-O2 phase transition and improved ion diffusion with Na+/vacancy disordering arrangement. The NCNMLO cathode exhibits a good cyclic stability with 70.8% of capacity retention at 1 C after 200 cycles and excellent rate capability with 40.1 mAh g-1 at 20 C. The dual sites doping strategy provides an effective and simple approach for designing high-performance layered oxide cathode materials for sodium-ion batteries.

Carbon, nitrogen and phosphorus contents and their ecological stoichiometric characteristics in leaf litter from the Jianfengling Tropical Montane Rainforest.

Investigating carbon (C), nitrogen (N) and phosphorus (P) contents and ecological stoichiometric characteristics in leaf litter from tropical rainforests is crucial for elucidating nutrient cycling and energy flow in forest ecosystems. In this study, a 60-ha tropical montane rainforest dynamic monitoring plot in Jianfengling, was selected as the research site and 60 subplots were selected for detailed study. Leaf litter was collected monthly throughout 2016, branches of similar height were placed atthe four corners of each sample square to support a nylon cloth (1 m× 1 m) with 1 mm apertures. The collected plant leaves were sorted,placed into envelopes, labelled, and transported to the laboratory and samples from various plant species were identified, resulting in a total of 107 samples collected and analyzed. For the 31 dominant species, the leaf litter had C, N and P contents of 312.71 ± 28.42, 4.95 ± 0.46 and 0.40 ± 0.03 g/kg, respectively. The C:N, C:P and N:P ratios were 63.61 ± 7.50, 790.91 ± 82.30 and 12.49 ± 1.00, respectively, indicating moderate variability. The C, N and P contents exhibited greater variability among the plant groups, indicating significant heterogeneity among the samples. In contrast, the data from the subplots exhibited less variability, highlighting significant homogeneity. Overall, the mean carbon, nitrogen and phosphorus contents in the leaf litter from tropical montane rainforests were lower than those observed at national and global scales. The N:P ratios in leaf litter below 14 indicated that nitrogen limited litter decomposition in Jianfengling. However, no significant correlations were observed between the C, N and P contents and their stoichiometric ratios in leaf litter and those in soil. The above results provide important reference data and scientific basis for the nutrient cycling and energy flow processes, and in the future, we can explore the limiting role and mechanism of nitrogen in the decomposition process of leaf litter.

Li3V2(PO4)3 sintering atmosphere optimisation for its integration in all-solid-state batteries

Integration of active materials into the architecture of all-solid-state batteries represents a significant scientific inquiry. Li3V2(PO4)3 (LVP), a positive and negative electrode active material for Li-ion batteries, has been subject to extensive research to elucidate its electrochemical behaviour during cycling processes. However, the comprehensive analysis of its thermal behaviour under different sintering atmosphere conditions has remained underexplored, particularly in the context of its compatibility with solid electrolytes. This study presents a meticulous study of sintering process under different atmospheres with precise control over oxygen partial pressure. Interestingly, we were able to sinter LVP and obtain dense, pure ceramic phase under slightly oxidising atmosphere, characterized by conductivity properties analogous to those observed in samples sintered under Ar/H2 conditions. The findings of this investigation contribute to the understanding of the optimal conditions required for the sintering of LVP, paving the way for the co-sintering of this material with inorganic solid electrolyte unstable under reducing atmosphere, such as LATP.

Manganese mineralization constrained by redox conditions in the Cryogenian Nanhua Basin, South China and its implications for nitrogen and carbon cycling

The Nanhua Basin of South China recorded complete Cryogenian stratigraphic sequence from the Sturtian Glaciation (~717–660 Ma) to the Marinoan Glaciation (~654–635 Ma). The interglacial Datangpo Fm in the Nanhua Basin is divided into two members, and the first member consists of the Mn-carbonate unit and the overlying black shale unit, containing a series of large and superlarge manganese deposits. The metallogenic process of manganese deposits is not clear, and the Mn-carbonates formed through the precursor of Mn-oxide/oxyhydroxide reduction or directly precipitated from an anoxic water column. Moreover, the redox conditions in the deep Nanhua Basin during the precipitation of manganese deposits are also controversial. In this study, the high-resolution nitrogen contents (TN), isotope compositions, carbon isotope compositions of organic and inorganic matter from the first member of the Datangpo Fm are analyzed. The δ15N values of the Mn-carbonate unit (+1.53‰ to +5.26‰, mean +3.36‰) are higher than those of the overlying black shale unit (−3.74‰ to +3.54‰, mean +0.89‰). The Mn contents show a negative relationship with TN but a positive relationship with δ15N in the Mn-carbonate unit, implying that the formation of Mn-carbonates is related to redox variations. The relatively higher δ15N values in the Mn-carbonate unit indicated oxic conditions, and NH4+can be released and partially oxidized during the mineralization of organic matter, resulting in the residual 15N-enriched NH4+ being transferred into clay minerals. Meanwhile, the lower δ15N values in the black shale unit indicated anoxic conditions, which recorded primary N isotope signals. The Mn-carbonate unit is characterized by negative δ13Ccarb values (−11.17‰ to −5.22‰, mean −8.30‰), which show a positive relationship with δ13Corg, but a negative relationship with Mn contents, implying that the negative δ13Ccarb excursions were related to the organic matter degradation during Mn-carbonate formation. The findings of this study indicated that the metallogenesis of manganese deposits in the Cryogenian Nanhua Basin was constrained mainly by the oxic interval in the deep basin. The nitrogen and carbon cycling process can provide new insights into geochemical cycling after the Sturtian Glaciation.

Lithium-rich manganese-based layered oxide cathode materials for lithium-ion batteries modified by MoS2 coatings with two-dimensional graphene-like structures

Lithium-rich manganese-based layered oxide cathode materials (LRMCs) have some unique advantages such as high theoretical capacity (≥ 250 mAh g−1) and high energy density. Therefore, they are deemed as a kind of cathode material for lithium-ion batteries with an excellent prospect of application. However, the redox of oxygen anion is able to generate irreversible lattice oxygen loss, leading to irreversible loss of capacity, bringing about a sharp drop of working voltage, and seriously restricting the commercialization of LRMCs. In this paper, MoS2 coating with two-dimensional graphene-like structure was coated on the surface of LRMCs materials for improving the cycling stability and rate performance. The MoS2 coating can provide a two-dimensional diffusion channel for the migration of lithium-ions, which facilitates the fast release of lithium-ions during cycling process. The results show that the first discharge capacity, initial Coulomb efficiency and rate performance of LRMCs are improved. When the current density is 1 C, the first discharge specific capacity of LRMCs@MoS2 reaches 227.69 mAh g−1, and the capacity retention ratio is 84.98 % after 100 cycles. When the current density is 5 C, it can still provide a discharge specific capacity of 137.87 mAh g−1, demonstrating excellent electrochemical performance. This study comes up a simple and practical idea to realize the modification of cathode materials for high performance lithium-ion batteries.

Seasonal dynamics of amino acids in the Southern Yellow Sea: Feedback on the mechanism of green tides caused by Ulva prolifera

The biogeochemical processes of amino acids in the Southern Yellow Sea (SYS) have become more dynamic under the influence of the world's largest-scale green tide. The potential relationship between amino acids and green tides has not been effectively assessed, despite its critical importance for exploring dissolved organic matter (DOM) cycling processes in marginal seas. In this study, three cruises were conducted to analyze the concentrations and compositions of total hydrolyzed amino acids (THAAs) in the SYS during the spring, summer, and autumn of 2019. The bioavailability potential of DOM was evaluated using the degradation index (DI) and THAA nitrogen normalized yield (THAA (%DON)) (DON as dissolved organic nitrogen). The variation dynamics of amino acid indicators during different stages of green tide were further explored. The results showed that the THAA concentrations and DOM bioavailability in the SYS were considerably influenced by biological processes. The THAA concentrations (0.96 ± 0.34 μmol L−1) exhibited the lowest mean values in the summer, while the DI values (0.106 ± 0.461) and mean THAA (%DON) values (18.20 ± 6.58 %) were the highest during this season. The distribution of amino acid indicators in the summer (the late-tide stage) was regulated by the green tide mechanism, and kept pace with the green tide floating region. In comparison with the waters in south of 35° N, the THAA concentrations and DI values experienced significant seasonal variations (p < 0.05) in north of 35° N, with the highest DI values (1.217) observed in the green tide aggregation area. This indicates the transformation of nutrient sources for Ulva prolifera in the late-tide stage and its impact on DOM bioavailability. Thus, as a potential feedback indicator of green tides, the study of amino acids is meaningful for understanding the occurrence of green tides and the source-sink pattern of organic nitrogen.