A data selection method for matrix effects and uncertainty reduction for laser-induced breakdown spectroscopy

Severe matrix effects and high signal uncertainty are two key bottlenecks for the quantitative performance and wide applications of laser-induced breakdown spectroscopy(LIBS).Based on the understanding that the superposition of both matrix effects and signal uncertainty directly affects plasma parameters and further influences spectral intensity and LIBS quantification performance,a data selection method based on plasma temperature matching(DSPTM)was proposed to reduce both matrix effects and signal uncertainty.By selecting spectra with smaller plasma temperature differences for all samples,the proposed method was able to build up the quantification model to rely more on spectra with smaller matrix effects and signal uncertainty,therefore improving final quantification performance.When applied to quantitative analysis of the zinc content in brass alloys,it was found that both accuracy and precision were improved using either a univariate model or multiple linear regression(MLR).More specifically,for the univariate model,the root-mean-square error of prediction(RMSEP),the determination coefficients(R^(2))and relative standard derivation(RSD)were improved from 3.30%,0.864 and 18.8%to 1.06%,0.986 and 13.5%,respectively;while for MLR,RMSEP,R^(2)and RSD were improved from 3.22%,0.871 and 26.2%to 1.07%,0.986 and 17.4%,respectively.These results prove that DSPTM can be used as an effective method to reduce matrix effects and improve repeatability by selecting reliable data.

A three-way electrolyte with ternary solvents for high-energy-density and long-cycling lithium-sulfur pouch cells

Lithium–sulfur(Li–S)batteries promise high-energy-density potential to exceed the commercialized lithiumion batteries but suffer from limited cycling lifespan due to the side reactions between lithium polysulfides(LiPSs)and Li metal anodes.Herein,a three-way electrolyte with ternary solvents is proposed to enable high-energy-density and long-cycling Li–S pouch cells.Concretely,ternary solvents composed of 1,2-dimethoxyethane,di-isopropyl sulfide,and 1,3,5-trioxane are employed to guarantee smooth cathode kinetics,inhibit the parasitic reactions,and construct a robust solid electrolyte interphase,respectively.The cycling lifespan of Li–S coin cells with 50μm Li anodes and 4.0 mg cm^(−2) sulfur cathodes is prolonged from88 to 222 cycles using the three-way electrolyte.Nano-heterogeneous solvation structure of LiPSs and organic-rich solid electrolyte interphase are identified to improve the cycling stability of Li metal anodes.Consequently,a 3.0 Ah-level Li–S pouch cell with the three-way electrolyte realizes a high energy density of 405 Wh kg^(−1) and undergoes 27 cycles.Thiswork affords a three-way electrolyte recipe for suppressing the side reactions of LiPSs and inspires rational electrolyte design for practical high-energy-density and long-cycling Li–S batteries.

In-situ determination of onset lithium plating for safe Li-ion batteries

Lithium plating in working batteries has attracted wide attention in the exploration of safe energy storage. Establishing an effective and rapid early-warning method is strongly considered but quite challenging since lithium plating behavior is determined by diverse factors. In this contribution, we present a non-destructive electrochemical detection method based on transient state analysis and threeelectrode cell configuration. Through dividing the iR drop value by the current density, the as-obtained impedance quantity(R_(i)) can serve as a descriptor to describe the change of electrochemical reaction impedance on the graphite anode. The onset of lithium plating can be identified from the sharp drop of R_(i). Once the dendritic plated lithium occurs, the extra electrochemical reactions at the lithium interfaces leads to growing active area and reduced surface resistance of the anode. We proposed a protocol to operate the batteries under the limited capacity, which renders the cell with 98.2% capacity retention after 1000 cycles without lithium plating. The early-warning method has also been validated in in-situ optical microscopy batteries and practical pouch cells, providing a general but effective method for online lithium plating detection towards safe batteries.

Roadmap for rechargeable batteries:present and beyond

Rechargeable batteries currently hold the largest share of the electrochemical energy storage market,and they play a major role in the sustainable energy transition and industrial decarbonization to respond to global climate change.Due to the increased popularity of consumer electronics and electric vehicles,lithium-ion batteries have quickly become the most successful rechargeable batteries in the past three decades,yet growing demands in diversified application scenarios call for new types of rechargeable batteries.Tremendous efforts are made to developing the next-generation post-Li-ion rechargeable batteries,which include,but are not limited to solid-state batteries,lithium–sulfur batteries,sodium-/potassium-ion batteries,organic batteries,magnesium-/zinc-ion batteries,aqueous batteries and flow batteries.Despite the great achievements,challenges persist in precise understandings about the electrochemical reaction and charge transfer process,and optimal design of key materials and interfaces in a battery.This roadmap tends to provide an overview about the current research progress,key challenges and future prospects of various types of rechargeable batteries.New computational methods for materials development,and characterization techniques will also be discussed as they play an important role in battery research.

Re-evaluating the nano-sized inorganic protective layer on Cu current collector for anode free lithium metal batteries

Anode free lithium metal batteries(AF-LMBs)have conspicuous advantages both in energy density and the compatibility of battery manufacturing process.However,the limited cycle life of AF-LMBs is a crucial factor hindering its practical application.Fluorinated or nitride artificial inorganic solid electrolyte interphase(SEI)has been found as an effective method to prolong the lifespan of AF-LMBs.Herein,by investigating the impact of nano-sized inorganic gradient layers(LiF or Li3N)on initial Li deposition behavior,we notice that the Li^(+) diffusion barrier and the deposition morphology are highly depended on the thickness of inorganic layers.Thicker protective layers cause larger overpotential as well as more aggregated Li^(+) distribution.This study reveals that the ideal SEI should be synthesized thin and uniformly enough and uncontrollable artificial SEI can cause damage to the lifespan of AF-LMBs.

Fertility and biochemical activity in sodic soils 17 years after reclamation with flue gas desulfurization gypsum

Previous studies have mainly focused on changes in soil physical and chemical properties to evaluate the reclamation of sodic soils using flue gas desulfurization(FGD)gypsum.However,information on the effects of this reclamation method on microbial-based indicators of soil quality is limited,particularly after many years of FGD gypsum application.This study aimed to investigate the long-term effects of FGD gypsum on soil organic carbon(SOC),nutrients,microbial biomass and enzyme activity.Data were collected from soils of three exchangeable sodium percentage(ESP)classes(i.e.,low-,middle-and hjgh-ESP classes of 6.1-20,20-30 and 30-78.4%,respectively)17 years after FGD gypsum treatment in Inner Mongolia,China.Averaged across the three ESP classes,FGD gypsum application increased the SOC contents at the 0-20 and 20-40-cm soil depths by 18 and 35%,respectively,and increased available potassium at the 0-20-cm soil depth by 51%compared with the no-gypsum controls.The microbial biomass carbon and microbial biomass nitrogen contents at the 20-40-cm soil depth increased by 69 and 194%,respectively,under FGD gypsum.Except in the high-ESP class,urease activities in the 0-40 cm soil profile were significantly higher in the FGD gypsum treatments than in the controls.A significant increase in alkaline phosphatase activity was concentrated in the 20-40 cm soil layer;few classes showed significant increases in catalase and invertase activities in the 0-20 cm soil layer.Pearson correlation analysis showed that increases in soil fertility and biological activity could be attributed to reductions in electrical conductivity,pH and ESP caused by FGD gypsum application.These results confirm that FGD gypsum application is a viable strategy for reclaiming sodic soils due to its positive effects on soil fertility and biochemistry and that it may contribute to soil ecosystem sustainability.

Polar interaction of polymer host-solvent enables stable solid electrolyte interphase in composite lithium metal anodes

The lithium(Li) metal anode is an integral component in an emerging high-energy-density rechargeable battery.A composite Li anode with a three-dimensional(3 D) host exhibits unique advantages in suppressing Li dendrites and maintaining dimensional stability.However,the fundamental understanding and regulation of solid electrolyte interphase(SEI),which directly dictates the behavior of Li plating/stripping,are rarely researched in composite Li metal anodes.Herein,the interaction between a polar polymer host and solvent molecules was proposed as an emerging but effective strategy to enable a stable SEI and a uniform Li deposition in a working battery.Fluoroethylene carbonate molecules in electrolytes are enriched in the vicinity of a polar polyacrylonitrile(PAN) host due to a strong dipole-dipole interaction,resulting in a LiF-rich SEI on Li metal to improve the uniformity of Li deposition.A composite Li anode with a PAN host delivers 145 cycles compared with 90 cycles when a non-polar host is employed.Moreover,60 cycles are demonstrated in a 1:0 Ah pouch cell without external pressure.This work provides a fresh guidance for designing practical composite Li anodes by unraveling the vital role of the synergy between a 3 D host and solvent molecules for regulating a robust SEI.

Electrolyte inhomogeneity induced lithium plating in fast charging lithium-ion batteries

Fast charging capability of lithium-ion batteries is in urgent need for widespread economic success of electric vehicles. However, the application of the fast charging technology often leads to the inevitable lithium plating on the graphite anode, which is one of the main culprits that endanger battery safety and shorten battery lifespan. The in-depth understanding of the initiation of lithium metal nucleation and the following plating behavior is a key to the development of fast charging cells. Herein, we investigate the overlooked effect of the non-uniform distribution of electrolyte on lithium plating during fast charging. Prior lithium plating occurs on the saturated lithium-graphite compounds in the anode region with sufficient electrolyte since the lithium-ion transport is blocked in the anode region lacking electrolyte. The uniform distribution of electrolyte is crucial for the construction of safe lithium-ion batteries especially in fast charging scenarios.

The application of molecular simulation in ash chemistry of coal

One of the crucial issues in modern ash chemistry is the realization of efficient and clean coal conversion.Industrially,large-scale coal gasification technology is well known as the foundation to improve the atom economy.In practice,the coal ash fusibility is a critical factor to determine steady operation standards of the gasifier,which is also the significant criterion to coal species selection for gasification.Since coal behaviors are resultant from various evolutions in different scales,the multi-scale understanding of the ash chemistry is of significance to guide the fusibility adjustment for coal gasification.Considering important roles of molecular simulation in exploring ash chemistry,this paper reviews the recent studies and developments on modeling of molecular systems for fusibility related ash chemistry for the first time.The discussions are emphasized on those performed by quantum mechanics and molecular mechanics,the two major simulation methods for microscopic systems,which may provide various insights into fusibility mechanism.This review article is expected to present comprehensive information for recent molecular simulations of coal chemistry so that new clues to find strategies controlling the ash fusion behavior can be obtained.

A robust solid electrolyte interphase enabled by solvate ionic liquid for high-performance sulfide-based all-solid-state lithium metal batteries

All-solid-state lithium metal batteries(ASSLMBs)that incorporate solid electrolyte(SE)and lithium metal anode suggest considerable potential in addressing the security concerns and energy density limitation of conventional lithium-ion batteries(LIBs).However,the practical application of ASSLMBs is always restricted by the interfacial instability of lithium metal anode/electrolyte and inevitable lithium dendrites propagation in SE.Herein,a solvate ionic liquid is adopted to modify the interface stability of lithium metal anode/electrolyte and inhibit the growth of lithium dendrites via an in-situ formation of a robust solid electrolyte interphase(SEI)on the surface of lithium metal anode.Consequently,the ASSLMBs assembled with Li_(6)PS_(5)Cl(LPSCl)electrolyte,lithium metal anode that protected by robust SEI layer,and LiNbO_(3)@NCM622 cathode exhibit high initial capacity of 126.5 mAh·g^(−1)and improved cycling stability with a capacity retention of 80.3%over 60 cycles at 0.1 C.This work helps to provide a facile route for the design of robust SEI in the application of ASSLMBs.

A review of solid-state lithium metal batteries through in-situ solidification

High-energy-density lithium metal batteries are the next-generation battery systems of choice,and replacing the flammable liquid electrolyte with a polymer solid-state electrolyte is a prominent conduct towards realizing the goal of high-safety and high-specific-energy devices.Unfortunately,the inherent intractable problems of poor solid-solid contacts between the electrode/electrolyte and the growth of Li dendrites hinder their practical applications.The in-situ solidification has demonstrated a variety of advantages in the application of polymer electrolytes and artificial interphase,including the design of integrated polymer electrolytes and asymmetric polymer electrolytes to enhance the compatibility of solid–solid contact and compatibility between various electrolytes,and the construction of artificial interphase between the Li anode and cathode to suppress the formation of Li dendrites and to enhance the high-voltage stability of polymer electrolytes.This review firstly elaborates the history of in-situ solidification for solid-state batteries,and then focuses on the synthetic methods of solidified electrolytes.Furthermore,the recent progress of in-situ solidification technology from both the design of polymer electrolytes and the construction of artificial interphase is summarized,and the importance of in-situ solidification technology in enhancing safety is emphasized.Finally,prospects,emerging challenges,and practical applications of in-situ solidification are envisioned.

Effect of ambient pressures on laser-induced breakdown spectroscopy signals

Laser-induced breakdown spectroscopy(LIBS)is regarded as the future superstar for analytical chemistry and widely applied in various fields.Improving the quality of LIBS signal is fundamental to achieving accurate quantification and large-scale commercialization of LIBS.To propose control methods that improve LIBS signal quality,it is essential to have a comprehensive understanding of the influence of key parameters,such as ambient gas pressure,temperature,and sample temperature on LIBS signals.To date,extensive research has been carried out.However,different researchers often yield significantly different experimental results for LIBS,preventing the formation of consistent conclusions.This greatly prevents the understanding of influencing laws of key parameters and the improvement of LIBS quantitative performance.Taking ambient gas pressure as an example,this paper compares the effects of ambient gas pressure under different optimization conditions,reveals the influence of spatiotemporal window caused by inherent characteristics of LIBS signal sources,i.e.,intense temporal changes and spatial non-uniformity of laser-induced plasmas,on the impact patterns of key parameters.From the perspective of plasma spatiotemporal evolution,the paper elucidates the influence patterns of ambient gas pressure on LIBS signals,clarifying seemingly contradictory research results in the literature.

Comparison of models to predict air infiltration rate of buildings with different surrounding environments

The air infiltration rate of buildings strongly influences indoor environment and energy consumption.In this study,several traditional methods for determining the air infiltration rate were compared,and their accuracy in different scenarios was examined.Additionally,a method combining computational flow dynamics(CFD)with the Swami and Chandra(S-C)model was developed to predict the influence of the surrounding environment on the air infiltration rate.Two buildings in Dalian,China,were selected:one with a simple surrounding environment and the other with a complex surrounding environment;their air infiltration rates were measured.The test results were used to validate the accuracy of the air infiltration rate solution models in different urban environments.For the building with a simple environment,the difference between the simulation and experimental results was 0.86%–22.52%.For the building with a complex environment,this difference ranged from 17.42%to 159.28%.We found that most traditional models provide accurate results for buildings with simple surrounding and that the simulation results widely vary for buildings with complex surrounding.The results of the method of combining CFD with the S-C model were more accurate,and the relative error between the simulation and test results was 10.61%.The results indicate that the environment around the building should be fully considered when calculating the air infiltration rate.The results of this study can guide the application of methods of determining air infiltration rate.

A calibration-free model for laser-induced breakdown spectroscopy using non-gated detectors

Calibration-free(CF)laser-induced breakdown spectroscopy(LIBS)is normally only applicable for gated detectors due to its dependence on the assumption of a steady-state plasma.However,most currently available LIBS systems are equipped with non-gated detectors such as chargecoupled device(CCD),which degrades the accuracy of CF method.In this paper,the reason for the less satisfactory quantification performance of CF for LIBS with non-gated detectors was clarified and a time-integration calibration-free(TICF)model was proposed for applications with non-gated detectors.It was based on an assumed temporal profile of plasma properties,including temperature and electron density,obtained from another pre-experiment.The line intensity at different time during the signal collection time window was estimated with self-absorption correction according to the temporal profile of the plasma properties.The proposed model was validated on titanium alloys and compared with traditional CF.The accuracy of elemental concentration measurement was improved significantly:the average relative error of aluminum and vanadium decreased from 6.07%and 22.34%to 2.01%and 1.92%,respectively.The quantification results showed that TICF method was able to extend the applicability of CF to LIBS with non-gated detectors.