Lignin-derived hard carbon anode with a robust solid electrolyte interphase for boosted sodium storage performance

Hard carbon is regarded as a promising anode candidate for sodium-ion batteries due to its low cost,relatively low working voltage,and satisfactory specific capacity.However,it still remains a challenge to obtain a high-performance hard carbon anode from cost-effective carbon sources.In addition,the solid electrolyte interphase(SEI)is subjected to continuous rupture during battery cycling,leading to fast capacity decay.Herein,a lignin-based hard carbon with robust SEI is developed to address these issues,effectively killing two birds with one stone.An innovative gas-phase removal-assisted aqueous washing strategy is developed to remove excessive sodium in the precursor to upcycle industrial lignin into high-value hard carbon,which demonstrated an ultrahigh sodium storage capacity of 359 mAh g^(-1).It is found that the residual sodium components from lignin on hard carbon act as active sites that controllably regulate the composition and morphology of SEI and guide homogeneous SEI growth by a near-shore aggregation mechanism to form thin,dense,and organic-rich SEI.Benefiting from these merits,the as-developed SEI shows fast Na+transfer at the interphases and enhanced structural stability,thus preventing SEI rupture and reformation,and ultimately leading to a comprehensive improvement in sodium storage performance.

Failure mechanism and infrared radiation characteristic of hard siltstone induced by stratification effect

The deformation in sedimentary rock induced by train loads has potential threat to the safe operation of tunnels. This study investigated the influence of stratification structure on the infrared radiation and temporal damage mechanism of hard siltstone. The uniaxial compression tests, coupled with acoustic emission(AE) and infrared radiation temperature(IRT) were conducted on siltstones with different stratification effects. The results revealed that the stratigraphic structure significantly affects the stress-strain response and strength degradation characteristics. The mechanical parameters exhibit anisotropy characteristics, and the stratification effect exhibits a negative correlation with the cracking stress and peak stress. The failure modes caused by the stratification effect show remarkable anisotropic features, including splitting failure(Ⅰ: 0°-22.50°, Ⅱ: 90°), composite failure(45°), and shearing failure(67.50°). The AE temporal sequences demonstrate a stepwise response characteristic to the loading stress level. The AE intensity indicates that the stress sensitivity of shearing failure and composite failure is generally greater than that of splitting failure. The IRT field has spatiotemporal migration and progressive dissimilation with stress loading and its dissimilation degree increases under higher stress levels. The stronger the stratification effect, the greater the dissimilation degree of the IRT field. The abnormal characteristic points of average infrared radiation temperature(AIRT) variance at local stress drop and peak stress can be used as early and late precursors to identify fracture instability. Theoretical analysis shows that the competitive relationship between compaction strengthening and fracturing damage intensifies the dissimilation of the infrared thermal field for an increasing stress level. The present study provides a theoretical reference for disaster warnings in hard sedimentary rock mass.

Free radicals trigger the closure of open pores in lignin-derived hard carbons toward improved sodium-storage capacity

The chemical activation of various precursors is effective for creating additional closed pores in hard carbons for sodium storage.However,the formation mechanism of closed pores under the influence of pore-forming agents is not well understood.Herein,an effective chemical activation followed by a high-temperature self-healing strategy is employed to generate interconnected closed pores in lignin-derived hard carbon(HCs).By systematic experimental design combined with electron paramagnetic res-onance spectroscopy,it can be found that the content of free radicals in the carbon matrix influences the closure of open pores at high temperatures.Excessively high activation temperature(>700 C)leads to a low free radical concentration,making it difficult to achieve self-healing of open pores at high tempera-tures.By activation at 700°C,a balance between pore making and self-healing is achieved in the final hard carbon.A large number of free radicals triggers rapid growth and aggregation of carbon microcrys-tals,blocking pre-formed open micropores and creating additional interconnected closed pores in as-obtained hard carbons.As a result,the optimized carbon anode(LK-700-1300)delivers a high reversible capacity of 330.8 mA h g^(-1) at 0.03 A g^(-1),which is an increase of 86 mA h g^(-1) compared to the pristine lignin-derived carbon anode(L-700-1300),and exhibits a good rate performance(202.1 mA h g^(-1) at 1 A g^(-1)).This work provides a universal and effective guidance for tuning closed pores of hard carbons from otherprecursors.

Modeling time-dependent mechanical behavior of hard rock considering excavation-induced damage and complex 3D stress states

To investigate the long-term stability of deep rocks,a three-dimensional(3D)time-dependent model that accounts for excavation-induced damage and complex stress state is developed.This model comprises three main components:a 3D viscoplastic isotropic constitutive relation that considers excavation damage and complex stress state,a quantitative relationship between critical irreversible deformation and complex stress state,and evolution characteristics of strength parameters.The proposed model is implemented in a self-developed numerical code,i.e.CASRock.The reliability of the model is validated through experiments.It is indicated that the time-dependent fracturing potential index(xTFPI)at a given time during the attenuation creep stage shows a negative correlation with the extent of excavationinduced damage.The time-dependent fracturing process of rock demonstrates a distinct interval effect of the intermediate principal stress,thereby highlighting the 3D stress-dependent characteristic of the model.Finally,the influence of excavation-induced damage and intermediate principal stress on the time-dependent fracturing characteristics of the surrounding rocks around the tunnel is discussed.

3D DEM simulation of hard rock fracture in deep tunnel excavation induced by changes in principal stress magnitude and orientation

To achieve the loading of the stress path of hard rock,the spherical discrete element model(DEM)and the new flexible membrane technology were utilized to realize the transient loading of three principal stresses with arbitrary magnitudes and orientations.Furthermore,based on the deep tunnel of China Jinping Underground Laboratory II(CJPL-II),the deformation and fracture evolution characteristics of deep hard rock induced by excavation stress path were analyzed,and the mechanisms of transient loading-unloading and stress rotation-induced fractures were revealed from a mesoscopic perspective.The results indicated that the stressestrain curve exhibits different trends and degrees of sudden changes when subjected to transient changes in principal stress,accompanied by sudden changes in strain rate.Stress rotation induces spatially directional deformation,resulting in fractures of different degrees and orientations,and increasing the degree of deformation anisotropy.The correlation between the degree of induced fracture and the unloading magnitude of minimum principal stress,as well as its initial level is significant and positive.The process of mechanical response during transient unloading exhibits clear nonlinearity and directivity.After transient unloading,both the minimum principal stress and minimum principal strain rate decrease sharply and then tend to stabilize.This occurs from the edge to the interior and from the direction of the minimum principal stress to the direction of the maximum principal stress on theε1-ε3 plane.Transient unloading will induce a tensile stress wave.The ability to induce fractures due to changes in principal stress magnitude,orientation and rotation paths gradually increases.The analysis indicates a positive correlation between the abrupt change amplitude of strain rate and the maximum unloading magnitude,which is determined by the magnitude and rotation of principal stress.A high tensile strain rate is more likely to induce fractures under low minimum principal stress.

Dynamic Analysis of A Deepwater Drilling Riser with A New Hang-off System

The safety of risers in hang-off states is a vital challenge in offshore oil and gas engineering.A new hang-off system installed on top of risers is proposed for improving the security of risers.This approach leads to a challenging problem:coupling the dynamics of risers with a new hang-off system combined with multiple structures and complex constraints.To accurately analyze the dynamic responses of the coupled system,a coupled dynamic model is established based on the Euler-Bernoulli beam-column theory and penalty function method.A comprehensive analysis method is proposed for coupled dynamic analysis by combining the finite element method and the Newmarkβmethod.An analysis program is also developed in MATLAB for dynamic simulation.The simulation results show that the dynamic performances of the risers at the top part are significantly improved by the new hang-off system,especially the novel design,which includes the centralizer and articulation joint.The bending moment and lateral deformation of the risers at the top part decrease,while the hang-off joint experiences a great bending moment at the bottom of the lateral restraint area which requires particular attention in design and application.The platform navigation speed range under the safety limits of risers expands with the new hang-off system in use.

A review of hard carbon anodes for rechargeable sodium-ion batteries

Hard carbons(HCs)are recognized as potential anode materials for sodium-ion batteries(SIBs)because of their low cost,environmental friendliness,and the abundance of their precursors.The presence of graphitic domains,numerous pores,and disordered carbon layers in HCs plays a significant role in determining their sodium storage ability,but these structural features depend on the precursor used.The influence of functional groups,including heteroatoms and oxygen-containing groups,and the microstructure of the precursor on the physical and electrochemical properties of the HC produced are evaluated,and the effects of carbonization conditions(carbonization temperature,heating rate and atmosphere)are also discussed.

THE SMOOTHING EFFECT IN SHARP GEVREY SPACE FOR THE SPATIALLY HOMOGENEOUS NON-CUTOFF BOLTZMANN EQUATIONS WITH A HARDPOTENTIAL

In this article, we study the smoothing effect of the Cauchy problem for the spatially homogeneous non-cutoff Boltzmann equation for hard potentials. It has long been suspected that the non-cutoff Boltzmann equation enjoys similar regularity properties as to whose of the fractional heat equation. We prove that any solution with mild regularity will become smooth in Gevrey class at positive time, with a sharp Gevrey index, depending on the angular singularity. Our proof relies on the elementary L^(2) weighted estimates.

Rational manipulation of electrolyte to induce homogeneous SEI on hard carbon anode for sodium-ion battery

Sodium-ion batteries (SIBs) have great potential to be the next major energy storage devices due to their obvious advantages and developing advanced electrodes and electrolytes is urgently necessary to promote its future industrialization.However,hard carbon as a state-of-the-art anode of SIBs still suffers from the low initial Coulomb efficiency and unsatisfactory rate capability,which could be improved by forming desirable solid electrolyte interphases (SEI) to some extent.Indeed,the chemistry and morphology of these interfacial layers are fundamental parameters affecting the overall battery operation,and optimizing the electrolyte to dictate the quality of SEI on hard carbon is a key strategy.Hence,this review summarizes the recent research on SEI design by electrolyte manipulation from solvents,salts,and additives.It also presents some potential mechanisms of SEI formation in various electrolyte systems.Besides,the current advanced characterization techniques for electrolyte and SEI structure analyses have been comprehensively discussed.Lastly,current challenges and future perspectives of SEI formation on hard carbon anode for SIBs are provided from the viewpoints of its compositions,evolution processes,structures,and characterization techniques,which will promote SEI efficient manipulation and improve the performance of hard carbon,and further contribute to the development of SIBs.

Synthesis strategies of hard carbon anodes for sodium-ion batteries

Sodium-ion battery(SIB)is an ideal candidate for large-scale energy storage due to high abundant sodium sources,relatively high energy density,and potentially low costs.Hard carbons,as one of the most promising anodes,could deliver high plateau capacities at low potentials,which boosts the energy densities of SIBs.Their slope capacities have been demonstrated from the defect adsorption of sodium ions,while the plateau capacity depends highly on intercalation and pore filling.Nevertheless,the specific structures of sodium ions stored in hard carbons have not been clarified,namely active sites of adsorption,intercalation,and pore-filling mechanisms.Therefore,delicate synthesis methods are required to prepare hard carbons with controllable specific structures,along with elucidating the precise active sites for enhancing the Na-ion storage performance.To offer databases for future designs,we summarized the synthesis strategies of hard carbon anodes for constructing active sites of plateau capacities.Synthesis methods were highlighted with corresponding influences on the meticulous structures of hard carbons and Na-ion storage behaviors.Last but not least,perspectives were proposed for developing hard carbon anodes from the points of research and practical applications.

High-efficiently doping nitrogen in kapok fiber-derived hard carbon used as anode materials for boosting rate performance of sodium-ion batteries

The engineering of plant-based precursor for nitrogen doping has become one of the most promising strategies to enhance rate capability of hard carbon materials for sodium-ion batteries;however,the poor rate performance is mainly caused by lack of pyridine nitrogen,which often tends to escape because of high temperature in preparation process of hard carbon.In this paper,a high-rate kapok fiber-derived hard carbon is fabricated by cross-linking carboxyl group in 2,6-pyridinedicarboxylic acid with the exposed hydroxyl group on alkalized kapok with assistance of zinc chloride.Specially,a high nitrogen doping content of 4.24%is achieved,most of which are pyridine nitrogen;this is crucial for improving the defect sites and electronic conductivity of hard carbon.The optimized carbon with feature of high nitrogen content,abundant functional groups,degree of disorder,and large layer spacing exhibits high capacity of 401.7 mAh g^(−1)at a current density of 0.05 A g^(−1),and more importantly,good rate performance,for example,even at the current density of 2 A g^(−1),a specific capacity of 159.5 mAh g^(−1)can be obtained.These findings make plant-based hard carbon a promising candidate for commercial application of sodium-ion batteries,achieving high-rate performance with the enhanced pre-cross-linking interaction between plant precursors and dopants to optimize aromatization process by auxiliary pyrolysis.

Assessment and control of the mine tremor disaster induced by the energy accumulation and dispersion of thick-hard roofs

In order to solve the problem that current theory models cannot accurately describe thick-hard roof(THR)elastic energy and assess the mine tremor disasters,a theoretical method,a Timoshenko beam theory on Winkler foundation was adopted to establish the THR’s periodic breaking model.The superposition principle was used for this complex model to derive the calculation formulas of the elastic energy and impact load on hydraulic supports.Then,the influence of roof thickness h,cantilever length L_(1),and load q on THR’s elastic energy and impact load was analyzed.And,the effect of mine tremor disasters was assessed.Finally,it is revealed that:(1)The THR’s elastic energy U exhibits power-law variations,with the fitted relationships U=0.0096L_(1)^(3.5866^),U=5943.9h^(-1.935),and U=21.049q^(2).(2)The impact load on hydraulic supports F_(ZJ) increases linearly with an increase in the cantilever length,thickness,and applied load.The fitted relationships are F_(ZJ)=1067.3L_(1)+6361.1,F_(ZJ)=125.89h+15100,and F_(ZJ)=10420q+3912.6.(3)Ground hydraulic fracturing and liquid explosive deep-hole blasting techniques effectively reduce the THR’s cantilever length at periodic breakages,thus eliminating mine tremor disasters.

Influencing factors analysis of hard limestone reformation and strength weakening under acidic effect

Roof disaster has always been an important factor restricting coal mine safety production.Acidic effect can reform the rock mass structure to weaken the macroscopic strength characteristics,which is an effective way to control the hard limestone roof.In this study,the effects of various factors on the reaction characteristics and mechanical properties of limestone were analyzed.The results show that the acid with stronger hydrogen production capacity after ionization(pK_(a)<0)has more prominent damage to the mineral grains of limestone.When pKa increases from−8.00 to 15.70,uniaxial compressive strength and elastic modulus of limestone increase by 117.22%and 75.98%.The influence of acid concentration is manifested in the dissolution behavior of mineral crystals,the crystal defects caused by large-scale acid action will lead to the deterioration of limestone strength,and the strength after 15%concentration reformation can be reduced by 59.42%.The effect of acidification time on limestone has stages and is the most obvious in the initial metathesis reaction stage(within 60 min).The key to the strength damage of acidified limestone is the participation of hydrogen ions in the reaction system.Based on the analytic hierarchy process method,the influence weights of acid type,acid concentration and acidification time on strength are 24.30%,59.54% and 16.16%,respectively.The research results provide theoretical support for the acidification control of hard limestone roofs in coal mines.

Deformation mechanism and roof pre-splitting control technology of gob-side entry in thick hard main roof full-mechanized longwall caving panel

This paper explores the deformation mechanism and control technology of roof pre-splitting for gob-side entries in hard roof full-mechanized longwall caving panel(LTCC).The investigation utilizes a comprehensive approach that integrates field monitoring,theoretical analysis,and numerical simulation.Theoretical analysis has illuminated the influence of the length of the lateral cantilever beam of the main roof(LCBM)above the roadway on the stability of the gob-side entry behind the panel.Numerical simulations have further revealed that the longer LCBM results in heightened vertical stress within the coal pillar,developed cracks around the roadway,and more pronounced damage to the roadway.Moreover,numerical simulations also demonstrate the potential of roof pre-splitting technology in optimizing the fracture position of the hard roof.This technology significantly reduces the length of the LCBM,thereby alleviating stress concentration in the coal pillars and integrated coal rib while minimizing the destruction of the gob-side entry.Therefore,this manuscript first proposes the use of roof pre-splitting technology to control roadway deformation,and automatically retain the entry within a hard roof LTCC panel.Field implementation has demonstrated that the proposed automatically retained entry by roof pre-splitting technology effectively reduces gob-side entry deformation and achieves automatically retained entry.

Regulating solid electrolyte interphase film on fluorinedoped hard carbon anode for sodium-ion battery

For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).

The hard X-ray nanoprobe beamline at the SSRF

The hard X-ray nanoprobe beamline BL13U is a phase-Ⅱ beamline project at the Shanghai Synchrotron Radiation Facility.The beamline aims to enable comprehensive experiments at high spatial resolutions ranging from 50 to 10 nm. The X-ray energy range of the beamline, 5–25 keV, can detect most elements in the periodic table. Two operating modes were designed to accommodate the experimental requirements of high-energy resolution or high photon flux, respectively. X-ray nanofluorescence, nanodiffraction, and coherent diffraction imaging are developed as the main experimental techniques for BL13U. This paper describes the beamline optics, end station configurations, experimental methods under development, and preliminary test results. This comprehensive overview aims to provide a clear understanding of the beamline capabilities and potential applications.

Hybrid hard carbon framework derived from polystyrene bearing distinct molecular crosslinking for enhanced sodium storage

Exploiting high-performance yet low-cost hard carbon anodes is crucial to advancing the state-of-the-art sodium-ion batteries.However,the achievement of superior initial Coulombic efficiency(ICE)and high Na-storage capacity via low-temperature carbonization remains challenging due to the presence of tremendous defects with few closed pores.Here,a facile hybrid carbon framework design is proposed from the polystyrene precursor bearing distinct molecular bridges at a low pyrolysis temperature of 800℃ via in situ fusion and embedding strategy.This is realized by integrating triazine-and carbonylcrosslinked polystyrene nanospheres during carbonization.The triazine crosslinking allows in situ fusion of spheres into layered carbon with low defects and abundant closed pores,which serves as a matrix for embedding the well-retained carbon spheres with nanopores/defects derived from carbonyl crosslinking.Therefore,the hybrid hard carbon with intimate interface showcases synergistic Na ions storage behavior,showing an ICE of 70.2%,a high capacity of 279.3 mAh g^(-1),and long-term 500 cycles,superior to carbons from the respective precursor and other reported carbons fabricated under the low carbonization temperature.The present protocol opens new avenues toward low-cost hard carbon anode materials for high-performance sodiumion batteries.

Gravel hardness effect on compaction characteristics of gravelly soil

The compaction characteristics of gravelly soil are affected by gravel hardness.To investigate the evolution and influencing mechanism of different gravel hardness on the compaction characteristics of gravelly soil,heavy compaction tests and crushing tests were conducted on gravelly soils with gravels originated from hard,soft and extremely soft rocks.According to orthogonal experiments and variance analysis,it was found that hardness has a significant impact on the maximum dry density of gravelly soil,followed by gravel content,and lastly,moisture content.For gravel compositions with an average saturated uniaxial compressive strength less than 60 MPa,the order of compacted maximum dry density is soft gravels>hard gravels>extremely soft gravels.Each type of gravelly soil has a threshold for gravel content,with 60%for hard and soft gravels and 50%for extremely soft gravels.Beyond these thresholds,the compacted dry density decreases significantly.There is a certain interaction between hardness,gravel content,and moisture content.Higher hardness increases the influence of gravel content,whereas lower hardness increases the influence of moisture content.Gravelly soils with the coarse aggregate(CA)between 0.7 and 0.8 typically achieve higher dry densities after compaction.In addition,the prediction equations for the particle breakage rate and CA ratio in the Bailey method were proposed to estimate the compaction performance of gravelly soil preliminarily.The results further revealed the compaction mechanism of different gravelly soils and can provide reference for subgrade filling construction.

Influence of heat input on microhardness and microstructure across the welding interface between stainless steel and low alloy steel

The welding interface is crucial to the service safety of dissimilar metal weld(DMW)joints between stainless steel(SS)and low alloy(LA)steel.Different status of welding interfaces was prepared by cladding SS consumables to LA steel substrates with different heat inputs via tungsten inert gas arc welding(TIG),followed by a series of microstructural characterizations and hardness tests.Results showed that a hardening and transition layer(TL)would be generated along the welding interface,and the width and hardening degree of the TL would increase with the heat input.Meanwhile,heavy load hardness tests showed that highly severe inhomogeneous plastic deformation and the microcrack would be generated in the interfacial region and the welding interface respectively in the highest heat input sample(1.03 kJ/mm).These results indicate that the increase in heat input would deteriorate the bonding performance of DMW joints.Further microstructural observations showed that the higher hardening degree of the highest heat input sample was mainly attributed to the stronger grain boundary,solution,and dislocation strengthening effects.

Physical and numerical investigations of target stratum selection for ground hydraulic fracturing of multiple hard roofs

Ground hydraulic fracturing plays a crucial role in controlling the far-field hard roof,making it imperative to identify the most suitable target stratum for effective control.Physical experiments are conducted based on engineering properties to simulate the gradual collapse of the roof during longwall top coal caving(LTCC).A numerical model is established using the material point method(MPM)and the strain-softening damage constitutive model according to the structure of the physical model.Numerical simulations are conducted to analyze the LTCC process under different hard roofs for ground hydraulic fracturing.The results show that ground hydraulic fracturing releases the energy and stress of the target stratum,resulting in a substantial lag in the fracturing of the overburden before collapse occurs in the hydraulic fracturing stratum.Ground hydraulic fracturing of a low hard roof reduces the lag effect of hydraulic fractures,dissipates the energy consumed by the fracture of the hard roof,and reduces the abutment stress.Therefore,it is advisable to prioritize the selection of the lower hard roof as the target stratum.