Aiming to obtain microwave absorbing materials with excellent mechanical and microwave absorption properties, carbon fiber reinforced Si3N4 ceramics(Cf-Si3N4) with pyrolytic carbon(PyC)/SiC interphases were fabricated...Aiming to obtain microwave absorbing materials with excellent mechanical and microwave absorption properties, carbon fiber reinforced Si3N4 ceramics(Cf-Si3N4) with pyrolytic carbon(PyC)/SiC interphases were fabricated by gel casting. The influences of carbon fibers content on mechanical and microwave absorption properties of as-prepared Si3N4 based ceramics were investigated. Results show that chemical compatibility between carbon fibers and Si3N4 matrix in high temperature environment can be significantly improved after introduction of Py C/SiC interphases. As carbon fibers content increases from 0 to 4 wt%, flexural strength of Si3N4 based ceramics decreases slightly while fracture toughness obviously increases. Moreover, both the real and imaginary parts of complex permittivity increase with the rising of carbon fibers content within the frequency range of 8.2–12.4 GHz. Investigation of microwave absorption shows that the microwave attenuation ability of Cf-Si3N4 ceramics with Py C/SiC interphases is remarkably enhanced compared with pure Si3N4 ceramics. Effective absorption bandwidth(<-10 d B) of10.17–12.4 GHz and the minimum reflection less of-19.6 d B are obtained for Si3N4 ceramics with 4 wt%carbon fibers in 2.0 mm thickness. Cf-Si3N4 ceramics with Py C/SiC interphases are promising candidates for microwave absorbing materials with favorable mechanical property.展开更多
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 hi...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.展开更多
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...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)).展开更多
Antimony sulfide(Sb_(2)S_(3))is a promising anode for lithium-ion batteries due to its high capacity and vast reserves.However,the low electronic conductivity and severe volume change during cycling hinder its commerc...Antimony sulfide(Sb_(2)S_(3))is a promising anode for lithium-ion batteries due to its high capacity and vast reserves.However,the low electronic conductivity and severe volume change during cycling hinder its commercialization.Herein our work,a three-dimensional(3D)Sb_(2)S_(3) thin film anode was fabricated via a simple vapor transport deposition system by using natural stibnite as raw material and stainless steel fiber-foil(SSF)as 3D current collector,and a carbon nanotube interphase was introduced onto the film surface by a simple dropping-heating process to promote the electrochemical performances.This 3D structure can greatly improve the initial coulombic efficiency to a record of 86.6% and high reversible rate capacity of 760.8 mAh·g^(-1) at 10 C.With carbon nanotubes interphase modified,the Sb_(2)S_(3) anode cycled extremely stable with high capacity retention of 94.7% after 160 cycles.This work sheds light on the economical preparation and performance optimization of Sb_(2)S_(3)-based anodes.展开更多
Interfacing and compatibility are the most challenging issues that affect the performance of polymer modified asphalt.Mechanisms of interfacial enhancement among four base asphalt components(asphaltenes,resins,aromati...Interfacing and compatibility are the most challenging issues that affect the performance of polymer modified asphalt.Mechanisms of interfacial enhancement among four base asphalt components(asphaltenes,resins,aromatics,and saturate),styrene-butadiene-styrene(SBS),and carbon nanotubes(CNTs)were investigated by molecular dynamics simulation,with the aim of understanding the key parameters that control the compatibility of CNTs and interphase behavior on the molecular scale.The compatibility of SBS-modified asphalt(SBSMA)was simulated based on self-assembly theory using indexes of binding energy,mean square displacement,diffusion coefficient,and relative concentration distribution.The interphase behavior and microstructure were observed by fluorescence microscopy and scanning electron microscopy.In addition,a rutting experiment was used to verify the molecular dynamics simulation based on macroscopic performance.The results showed that after adding CNTs,the binding energy of the SBS and aromatics increased from 301.8343 to 327.1102 kcal/mol.The diffusion coefficient of the SBS and asphaltenes decreased more than 3.2×10-11 m2/s,and the correlation coefficients between the diffusion coefficient and the molecular weight,surface area and volume were all lower than 0.3.Relative concentration distribution curves indicated that CNTs promote the ability of SBS to swell.Microscopic observations demonstrated that the swelling ability of SBS was increased by CNTs.Overall,the interphase of SBSMA was improved by the additional reinforcement,swelling,and diffusion provided by CNTs.Finally,the rutting experiment found that no matter what the temperature,the rutting factor of CNT/SBSMA is higher than that of SBSMA,which corroborates the findings from the molecular dynamics simulations.展开更多
Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interph...Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interphase(SEI).It is well known that the addition of flouroethylene carbonate(FEC)in the carbonate electrolyte is helpful to improve the cyclic performance of the Si anode.The possible origin is suggested to relate to the modification of the SEI.However,detailed information is still absent.In this work,the structural and mechanical properties of the SEI on Si thin film anode in the ethylene-carbonate-based(EC-based)and FEC-based electrolytes at different discharging and charging states have been investigated using a scanning atomic force microscopy force spectroscopy(AFMFS)method.Single-layered,double-layered,and multi-layered SEI structures with various Young’s moduli have been visualized three dimensionally at nanoscale based on the hundreds of force curves in certain scanned area.The coverage of the SEI can be obtained quantitatively from the two-dimensional(2D)project plots.The related analysis indicates that more soft SEI layers are covered on the Si anode,and this could explain the benefits of the FEC additive.展开更多
The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dea...The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.展开更多
Silicon(Si)is a potential high-capacity anode material for the next-generation lithium-ion battery with high energy density.However,Si anodes suff er from severe interfacial chemistry issues,such as side reactions at ...Silicon(Si)is a potential high-capacity anode material for the next-generation lithium-ion battery with high energy density.However,Si anodes suff er from severe interfacial chemistry issues,such as side reactions at the electrode/electrolyte interface,leading to poor electrochemical cycling stability.Herein,we demonstrate the fabrication of a conformal fl uorine-containing carbon(FC)layer on Si particles(Si-FC)and its in situ electrochemical conversion into a LiF-rich carbon layer above 1.5 V(vs.Li^(+)/Li).The as-formed LiF-rich carbon layer not only isolates the active Si and electrolytes,leading to the suppression of side reactions,but also induces the formation of a robust solid-electrolyte interface(SEI),leading to the stable interfacial chemistry of as-designed Si-FC particles.The Si-FC electrode has a high initial Coulombic effi ciency(CE)of 84.8%and a high reversible capacity of 1450 mAh/g at 0.4 C(1000 mA/g)for 300 cycles.In addition,a hybrid electrode consisting of 85 wt%graphite and 15 wt%Si-FC,and mass 2.3 mg/cm^(2) loading delivers a high areal capacity of 2.0 mAh/cm^(2) and a high-capacity retention of 93.2%after 100 cycles,showing the prospects for practical use.展开更多
Hard carbon (HC) has been considered as promising anode material for sodium-ion batteries (SIBs).The optimization of hard carbon’s microstructure and solid electrolyte interface (SEI) property are demonstrated effect...Hard carbon (HC) has been considered as promising anode material for sodium-ion batteries (SIBs).The optimization of hard carbon’s microstructure and solid electrolyte interface (SEI) property are demonstrated effective in enhancing the Na+storage capability,however,a one-step regulation strategy to achieve simultaneous multi-scale structures optimization is highly desirable.Herein,we have systematically investigated the effects of boron doping on hard carbon’s microstructure and interface chemistry.A variety of structure characterizations show that appropriate amount of boron doping can increase the size of closed pores via rearrangement of carbon layers with improved graphitization degree,which provides more Na+storage sites.In-situ Fourier transform infrared spectroscopy/electrochemical impedance spectroscopy (FTIR/EIS) and X-ray photoelectron spectroscopy (XPS) analysis demonstrate the presence of more BC3and less B–C–O structures that result in enhanced ion diffusion kinetics and the formation of inorganic rich and robust SEI,which leads to facilitated charge transfer and excellent rate performance.As a result,the hard carbon anode with optimized boron doping content exhibits enhanced rate and cycling performance.In general,this work unravels the critical role of boron doping in optimizing the pore structure,interface chemistry and diffusion kinetics of hard carbon,which enables rational design of sodium-ion battery anode with enhanced Na+storage performance.展开更多
Solid-state batteries(SSBs)with high-capacity Si anodes have been regarded as one of the most promising candidates to meet the large scale energy storage and electrical vehicles due to its intrinsic safety and potenti...Solid-state batteries(SSBs)with high-capacity Si anodes have been regarded as one of the most promising candidates to meet the large scale energy storage and electrical vehicles due to its intrinsic safety and potential high energy density.However,Si suffers from poor electrical conductivity and huge volume change and particles fracture during lithiaiotn and delithiation,which induces low practical energy density.In addition,the SSBs are often operated at high temperature due to the poor physical contact and huge resistance between Si and solid-state electrolyte(SSE).To improve the bulk electronic/ionic conductivity of Si and its interfacial compatibility with SSE,herein,a binder free and self-supporting Si/C film was developed.The monolithic carbon not only enhance the electric conductivity but also release huge stress during lithiation and delithiation.In addition,paired with the flexible and soft poly(vinylidene fluoride)-co-hexafluoropropylene(PVDF-HFP)and Li_(1.3)A_(l0.3)Ti_(1.7)(PO_(4))_(3)(LATP)solid-state electrolyte,a LiF-rich and electrochemical stable solid-electrolyte interphase(SEI)layer is in-situ engineered.The fast bulk and interfacial ionic transportation as well as the mechanical integrity of MSi enable high performance SSBs at room temperature.As a result,high specific capacity of 2137 m Ah/g with an initial Coulombic efficiency of 83.2%is obtained at a rate of 0.5 A/g.Even at a high rate of 3 A/g,the specific capacity is1793 m Ah/g.At a rate of 1 A/g,the Si/C anode delivers a long cycling performance over 500 cycles while maintains a capacity of 1135 mAh/g.This work provides a new strategy that combines charge transfer kinetics and interfacial chemistry design toward high energy density Si-based SSBs.展开更多
Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with t...Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with the coating of N-doped carbon are modified on the surface of carbon cloth(NCHZS@CC) to serve as the host material for Li metal.It is revealed that the high surface area of NCHZS@CC can significantly reduce local current density and mitigate volume change during cycling.More importantly,the lithiated product of ZnS,confined within the carbon cage,facilitates the uniform deposition of Li metal on carbon fibers and promotes the formation of a stable solid electrolyte interphase enriched with Li_(2)S,thereby improving long-term performance as the cycling progresses.Consequently,the LMAs based on NCHZS@CC demonstrate an impressive cycle life beyond560 h with an ultralow overpotential of 38 mV at a current density of 5 mA cm^(-2)with a capacity of 1 mAh cm^(-2)in the symmetric cell.In addition,when matched with a high mass loading cathode of LiFePO_(4)(11.5 mg cm^(-2)),the assembled full cell displays outstanding performance,achieving 900 cycles at a rate of 2C.展开更多
Carbonaceous cathode materials were prepared by a low-cost and facile molten salt carbonization of lotus stalks in molten carbonates at 850℃for aqueous zinc-ion hybrid supercapacitors(ZHSCs).The lotus stalk-derived c...Carbonaceous cathode materials were prepared by a low-cost and facile molten salt carbonization of lotus stalks in molten carbonates at 850℃for aqueous zinc-ion hybrid supercapacitors(ZHSCs).The lotus stalk-derived carbon by carbonization of one hour displayed excellent capacitive performance benefits from the comprehensive effect of hierarchically porous structure with large SSA,more mesopores,good electrical conductivity and high heteroatom doping.Coin-type ZHSCs deliver 164.4 F·g^(-1)at 0.2 A·g^(-1)and 70.0 F·g^(-1)at 20 A·g^(-1)with capacitance retention of 42.6%assembled with carbonic cathode and Zn@Zn_(3)(PO_(4))_(2)anode using 2 M ZnSO4 solution as electrolyte.Moreover,coin-type ZHSCs deliver the maximum energy density of 65.0 Wh·kg^(-1)at 168.7 W·kg^(-1)and the maximum power density of 11.4 kW·kg^(-1)at 12.7 Wh·kg^(-1).Thanks to the multifunctional Zn_(3)(PO_(4))_(2)interphase as Zn^(2+)-transfer ionic conductor and physical barrier.Moreover,coin-type ZHSCs exhibit outstanding recyclability with capacitance retention of 97.5%and coulombic efficiency of 100%after 10000 charge-discharge cycles at 1 A·g^(-1).展开更多
Owing to their very high theoretical capacity, lithium （Li） metal anodes regain widespread attentions for their promising applications for next-generation high-energy-density Li batteries （e.g., lithium-sulfur batt...Owing to their very high theoretical capacity, lithium （Li） metal anodes regain widespread attentions for their promising applications for next-generation high-energy-density Li batteries （e.g., lithium-sulfur batteries, lithium-oxygen batteries, solid-state lithium metal batter- ies）. However, the inherent bottleneck of Li metal anodes, especially the growth of Li dendrites and the related safety concerns, should be well addressed. Owing to their featured micro-/nano-porous structures and intriguing physical properties, nanocarbon materials have been applied as host materials for Li metal anodes. This review summarizes the recent progress in the development of porous nanocarbon materials for safe Li metal anodes. The perspectives regarding the challenges and future development of employing micro-/nano-porous carbon materials in Li metal anodes are also included.展开更多
Carbon nanotubes (CNTs) are a class of carbon allotropes with interesting properties that make them productive materials for usage in various disciplines of nanotechnology such as in electronics equipments, optics and...Carbon nanotubes (CNTs) are a class of carbon allotropes with interesting properties that make them productive materials for usage in various disciplines of nanotechnology such as in electronics equipments, optics and therapeutics. They exhibit distinguished properties viz., strength, and high electrical and heat conductivity. Their uniqueness can be attributed due to the bonding pattern present between the atoms which are very strong and also exhibit high extreme aspect ratios. CNTs are classified as singlewalled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) on the basis of number of sidewalls present and the way they are arranged spatially. Application of CNTs to improve the performance of many products, especially in healthcare, has led to an occupational and public exposure to these nanomaterials. Hence, it becomes a major concern to analyze the issues pertaining to the toxicity of CNTs and find the best suitable ways to counter those challenges. This review summarizes the toxicity issues of CNTs in vitro and in vivo in different organ systems (bio interphases) of the body that result in cellular toxicity.展开更多
Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-pot...Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.展开更多
Ionic liquids have been paid much attention and are considered to replace the conventional organic electrolyte and solve the safety issues by virtue of nonvolatility,non-flammability,high ionic conductivity and extend...Ionic liquids have been paid much attention and are considered to replace the conventional organic electrolyte and solve the safety issues by virtue of nonvolatility,non-flammability,high ionic conductivity and extended electrochemical steady window.The paper introduces ionic liquids electrolyte on basis of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI),which shows a wide electrochemical window (0.5-4.5 V vs.Li+/Li),and is theoretically feasible as an electrolyte for Li/LiFePO4batteries to improve the safety.Linear sweep voltammetry (LSV) was performed to investigate the electrochemical stability window of the polymer electrolyte.Interfacial resistance for Li/electrolyte/Li symmetric cells and Li/electrolyte/LiFePO4 cells were studied by electrochemical impedance spectroscopy (EIS).The results showed that additive vinylene carbonate (VC) enhances the formation of solid electrolyte interphase film to protect lithium anodes from corrosion and improves the compatibility of ionic liquid electrolyte towards lithium anodes.Accordingly,Li/LiFePO4cells delivers the initial discharge capacity of 124 mAh g-1 at a current rate of 0.1C in the ionic liquid electrolyte (EMITFSI+0.8 mol L-1LiTFSI+5 wt%VC),and shows better cyclability than in the ionic liquid electrolyte without VC.展开更多
基金supported by the National Natural Science Foundation of China (Grant No. 51604107)the Natural Science Foundation of Hunan Province (Grant No. 2019JJ50115 and 2019JJ50768)
文摘Aiming to obtain microwave absorbing materials with excellent mechanical and microwave absorption properties, carbon fiber reinforced Si3N4 ceramics(Cf-Si3N4) with pyrolytic carbon(PyC)/SiC interphases were fabricated by gel casting. The influences of carbon fibers content on mechanical and microwave absorption properties of as-prepared Si3N4 based ceramics were investigated. Results show that chemical compatibility between carbon fibers and Si3N4 matrix in high temperature environment can be significantly improved after introduction of Py C/SiC interphases. As carbon fibers content increases from 0 to 4 wt%, flexural strength of Si3N4 based ceramics decreases slightly while fracture toughness obviously increases. Moreover, both the real and imaginary parts of complex permittivity increase with the rising of carbon fibers content within the frequency range of 8.2–12.4 GHz. Investigation of microwave absorption shows that the microwave attenuation ability of Cf-Si3N4 ceramics with Py C/SiC interphases is remarkably enhanced compared with pure Si3N4 ceramics. Effective absorption bandwidth(<-10 d B) of10.17–12.4 GHz and the minimum reflection less of-19.6 d B are obtained for Si3N4 ceramics with 4 wt%carbon fibers in 2.0 mm thickness. Cf-Si3N4 ceramics with Py C/SiC interphases are promising candidates for microwave absorbing materials with favorable mechanical property.
基金The authors are grateful for the grants provided by the National Natural Science Foundation of China(Grant no.52274309)the Postgraduate Scientific Research Innovation Project of Hunan Province(Grant no.CX20220183)Simin Li thanks the National Natural Science Foundation of China(Grant no.52204327).
文摘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.
基金National Key R&D Program of China,Grant/Award Number:2022YFB4000120Fundamental Research Funds for the Central Universities,Grant/Award Number:2022ZYGXZR101。
文摘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)).
基金financially supported by the National Natural Science Foundation of China(No.51774343).
文摘Antimony sulfide(Sb_(2)S_(3))is a promising anode for lithium-ion batteries due to its high capacity and vast reserves.However,the low electronic conductivity and severe volume change during cycling hinder its commercialization.Herein our work,a three-dimensional(3D)Sb_(2)S_(3) thin film anode was fabricated via a simple vapor transport deposition system by using natural stibnite as raw material and stainless steel fiber-foil(SSF)as 3D current collector,and a carbon nanotube interphase was introduced onto the film surface by a simple dropping-heating process to promote the electrochemical performances.This 3D structure can greatly improve the initial coulombic efficiency to a record of 86.6% and high reversible rate capacity of 760.8 mAh·g^(-1) at 10 C.With carbon nanotubes interphase modified,the Sb_(2)S_(3) anode cycled extremely stable with high capacity retention of 94.7% after 160 cycles.This work sheds light on the economical preparation and performance optimization of Sb_(2)S_(3)-based anodes.
基金the Innovative Funds Plan of Henan University of Technology(Nos.2020ZKCJ05 and 2020ZKCJ22)the Science and Technology Planning Project of Henan Province(No.192102310229)+4 种基金the Cultivation Plan for Youth Backbone Teachers of Institution of Higher Education by Henan Province(No.2019GGJS086)the Cultivation Plan for Youth Backbone Teachers by Henan University of Technologythe Key Science and Technology Research Project of Henan Provincial Department of Education(No.21A580002)the Foundation for Distinguished Young Talents of Henan University of Technology(No.2018QNJH09)the Central Public-interest Scientific Institution Basal Research Fund(No.2020–9049),China。
文摘Interfacing and compatibility are the most challenging issues that affect the performance of polymer modified asphalt.Mechanisms of interfacial enhancement among four base asphalt components(asphaltenes,resins,aromatics,and saturate),styrene-butadiene-styrene(SBS),and carbon nanotubes(CNTs)were investigated by molecular dynamics simulation,with the aim of understanding the key parameters that control the compatibility of CNTs and interphase behavior on the molecular scale.The compatibility of SBS-modified asphalt(SBSMA)was simulated based on self-assembly theory using indexes of binding energy,mean square displacement,diffusion coefficient,and relative concentration distribution.The interphase behavior and microstructure were observed by fluorescence microscopy and scanning electron microscopy.In addition,a rutting experiment was used to verify the molecular dynamics simulation based on macroscopic performance.The results showed that after adding CNTs,the binding energy of the SBS and aromatics increased from 301.8343 to 327.1102 kcal/mol.The diffusion coefficient of the SBS and asphaltenes decreased more than 3.2×10-11 m2/s,and the correlation coefficients between the diffusion coefficient and the molecular weight,surface area and volume were all lower than 0.3.Relative concentration distribution curves indicated that CNTs promote the ability of SBS to swell.Microscopic observations demonstrated that the swelling ability of SBS was increased by CNTs.Overall,the interphase of SBSMA was improved by the additional reinforcement,swelling,and diffusion provided by CNTs.Finally,the rutting experiment found that no matter what the temperature,the rutting factor of CNT/SBSMA is higher than that of SBSMA,which corroborates the findings from the molecular dynamics simulations.
基金Project supported by the State Grid Technology Project,China(Grant No.DG71-17-010)。
文摘Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interphase(SEI).It is well known that the addition of flouroethylene carbonate(FEC)in the carbonate electrolyte is helpful to improve the cyclic performance of the Si anode.The possible origin is suggested to relate to the modification of the SEI.However,detailed information is still absent.In this work,the structural and mechanical properties of the SEI on Si thin film anode in the ethylene-carbonate-based(EC-based)and FEC-based electrolytes at different discharging and charging states have been investigated using a scanning atomic force microscopy force spectroscopy(AFMFS)method.Single-layered,double-layered,and multi-layered SEI structures with various Young’s moduli have been visualized three dimensionally at nanoscale based on the hundreds of force curves in certain scanned area.The coverage of the SEI can be obtained quantitatively from the two-dimensional(2D)project plots.The related analysis indicates that more soft SEI layers are covered on the Si anode,and this could explain the benefits of the FEC additive.
基金supported by the National Key Research and Development Program of China(2021YFB2400200)the National Natural Science Foundation of China(52104313,22172117,52072298)the Scientific Research Program of Shaanxi Provincial Education Department(21JK0808)。
文摘The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.
基金supported by the Innovation Fund of Wuhan National Laboratory for Optoelectronics of Huazhong University of Science and Technology.
文摘Silicon(Si)is a potential high-capacity anode material for the next-generation lithium-ion battery with high energy density.However,Si anodes suff er from severe interfacial chemistry issues,such as side reactions at the electrode/electrolyte interface,leading to poor electrochemical cycling stability.Herein,we demonstrate the fabrication of a conformal fl uorine-containing carbon(FC)layer on Si particles(Si-FC)and its in situ electrochemical conversion into a LiF-rich carbon layer above 1.5 V(vs.Li^(+)/Li).The as-formed LiF-rich carbon layer not only isolates the active Si and electrolytes,leading to the suppression of side reactions,but also induces the formation of a robust solid-electrolyte interface(SEI),leading to the stable interfacial chemistry of as-designed Si-FC particles.The Si-FC electrode has a high initial Coulombic effi ciency(CE)of 84.8%and a high reversible capacity of 1450 mAh/g at 0.4 C(1000 mA/g)for 300 cycles.In addition,a hybrid electrode consisting of 85 wt%graphite and 15 wt%Si-FC,and mass 2.3 mg/cm^(2) loading delivers a high areal capacity of 2.0 mAh/cm^(2) and a high-capacity retention of 93.2%after 100 cycles,showing the prospects for practical use.
基金National Key Research and Development Program of China (2022YFE0206300)National Natural Science Foundation of China (U21A2081,22075074, 22209047)+3 种基金Guangdong Basic and Applied Basic Research Foundation (2024A1515011620)Hunan Provincial Natural Science Foundation of China (2024JJ5068)Foundation of Yuelushan Center for Industrial Innovation (2023YCII0119)Student Innovation Training Program (S202410532594,S202410532357)。
文摘Hard carbon (HC) has been considered as promising anode material for sodium-ion batteries (SIBs).The optimization of hard carbon’s microstructure and solid electrolyte interface (SEI) property are demonstrated effective in enhancing the Na+storage capability,however,a one-step regulation strategy to achieve simultaneous multi-scale structures optimization is highly desirable.Herein,we have systematically investigated the effects of boron doping on hard carbon’s microstructure and interface chemistry.A variety of structure characterizations show that appropriate amount of boron doping can increase the size of closed pores via rearrangement of carbon layers with improved graphitization degree,which provides more Na+storage sites.In-situ Fourier transform infrared spectroscopy/electrochemical impedance spectroscopy (FTIR/EIS) and X-ray photoelectron spectroscopy (XPS) analysis demonstrate the presence of more BC3and less B–C–O structures that result in enhanced ion diffusion kinetics and the formation of inorganic rich and robust SEI,which leads to facilitated charge transfer and excellent rate performance.As a result,the hard carbon anode with optimized boron doping content exhibits enhanced rate and cycling performance.In general,this work unravels the critical role of boron doping in optimizing the pore structure,interface chemistry and diffusion kinetics of hard carbon,which enables rational design of sodium-ion battery anode with enhanced Na+storage performance.
基金financially supported by the Natural Science Foundation of Fujian Province(No.2021J01333)the funding from the Fujian Education Department of China(No.JAT210582)。
文摘Solid-state batteries(SSBs)with high-capacity Si anodes have been regarded as one of the most promising candidates to meet the large scale energy storage and electrical vehicles due to its intrinsic safety and potential high energy density.However,Si suffers from poor electrical conductivity and huge volume change and particles fracture during lithiaiotn and delithiation,which induces low practical energy density.In addition,the SSBs are often operated at high temperature due to the poor physical contact and huge resistance between Si and solid-state electrolyte(SSE).To improve the bulk electronic/ionic conductivity of Si and its interfacial compatibility with SSE,herein,a binder free and self-supporting Si/C film was developed.The monolithic carbon not only enhance the electric conductivity but also release huge stress during lithiation and delithiation.In addition,paired with the flexible and soft poly(vinylidene fluoride)-co-hexafluoropropylene(PVDF-HFP)and Li_(1.3)A_(l0.3)Ti_(1.7)(PO_(4))_(3)(LATP)solid-state electrolyte,a LiF-rich and electrochemical stable solid-electrolyte interphase(SEI)layer is in-situ engineered.The fast bulk and interfacial ionic transportation as well as the mechanical integrity of MSi enable high performance SSBs at room temperature.As a result,high specific capacity of 2137 m Ah/g with an initial Coulombic efficiency of 83.2%is obtained at a rate of 0.5 A/g.Even at a high rate of 3 A/g,the specific capacity is1793 m Ah/g.At a rate of 1 A/g,the Si/C anode delivers a long cycling performance over 500 cycles while maintains a capacity of 1135 mAh/g.This work provides a new strategy that combines charge transfer kinetics and interfacial chemistry design toward high energy density Si-based SSBs.
基金financial supports from the National Natural Science Foundation of China(Nos.22279116 and U20A20253)the Natural Science Foundation of Zhejiang Province(Nos.LQ24E020012 and LD22E020006)Jianbing Science and Technology Project of Zhejiang Province(No.2023C01127)
文摘Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with the coating of N-doped carbon are modified on the surface of carbon cloth(NCHZS@CC) to serve as the host material for Li metal.It is revealed that the high surface area of NCHZS@CC can significantly reduce local current density and mitigate volume change during cycling.More importantly,the lithiated product of ZnS,confined within the carbon cage,facilitates the uniform deposition of Li metal on carbon fibers and promotes the formation of a stable solid electrolyte interphase enriched with Li_(2)S,thereby improving long-term performance as the cycling progresses.Consequently,the LMAs based on NCHZS@CC demonstrate an impressive cycle life beyond560 h with an ultralow overpotential of 38 mV at a current density of 5 mA cm^(-2)with a capacity of 1 mAh cm^(-2)in the symmetric cell.In addition,when matched with a high mass loading cathode of LiFePO_(4)(11.5 mg cm^(-2)),the assembled full cell displays outstanding performance,achieving 900 cycles at a rate of 2C.
基金Funded by the Natural Science Foundation of Hubei Province(No.2024AFB930)the Scientific Research Project of Department of Education of Hubei Province(No.B2022096)+2 种基金the Scientific Research Project of Enshi Tujia&Miao Autonomous Prefecture(No.D20220073)the Open Fund of Hubei Key Laboratory of Biological Resources Protection and Utilization(Hubei Minzu University)(No.PT012210)the Hengsheng Industry Donation Fund(No.2025001)。
文摘Carbonaceous cathode materials were prepared by a low-cost and facile molten salt carbonization of lotus stalks in molten carbonates at 850℃for aqueous zinc-ion hybrid supercapacitors(ZHSCs).The lotus stalk-derived carbon by carbonization of one hour displayed excellent capacitive performance benefits from the comprehensive effect of hierarchically porous structure with large SSA,more mesopores,good electrical conductivity and high heteroatom doping.Coin-type ZHSCs deliver 164.4 F·g^(-1)at 0.2 A·g^(-1)and 70.0 F·g^(-1)at 20 A·g^(-1)with capacitance retention of 42.6%assembled with carbonic cathode and Zn@Zn_(3)(PO_(4))_(2)anode using 2 M ZnSO4 solution as electrolyte.Moreover,coin-type ZHSCs deliver the maximum energy density of 65.0 Wh·kg^(-1)at 168.7 W·kg^(-1)and the maximum power density of 11.4 kW·kg^(-1)at 12.7 Wh·kg^(-1).Thanks to the multifunctional Zn_(3)(PO_(4))_(2)interphase as Zn^(2+)-transfer ionic conductor and physical barrier.Moreover,coin-type ZHSCs exhibit outstanding recyclability with capacitance retention of 97.5%and coulombic efficiency of 100%after 10000 charge-discharge cycles at 1 A·g^(-1).
基金financially supported by the National Key Research and Development Program(Nos.2016YFA0202500,2015CB932500)the National Natural Scientific Foundation of China(Nos.21676160,21561130151)
文摘Owing to their very high theoretical capacity, lithium （Li） metal anodes regain widespread attentions for their promising applications for next-generation high-energy-density Li batteries （e.g., lithium-sulfur batteries, lithium-oxygen batteries, solid-state lithium metal batter- ies）. However, the inherent bottleneck of Li metal anodes, especially the growth of Li dendrites and the related safety concerns, should be well addressed. Owing to their featured micro-/nano-porous structures and intriguing physical properties, nanocarbon materials have been applied as host materials for Li metal anodes. This review summarizes the recent progress in the development of porous nanocarbon materials for safe Li metal anodes. The perspectives regarding the challenges and future development of employing micro-/nano-porous carbon materials in Li metal anodes are also included.
文摘Carbon nanotubes (CNTs) are a class of carbon allotropes with interesting properties that make them productive materials for usage in various disciplines of nanotechnology such as in electronics equipments, optics and therapeutics. They exhibit distinguished properties viz., strength, and high electrical and heat conductivity. Their uniqueness can be attributed due to the bonding pattern present between the atoms which are very strong and also exhibit high extreme aspect ratios. CNTs are classified as singlewalled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) on the basis of number of sidewalls present and the way they are arranged spatially. Application of CNTs to improve the performance of many products, especially in healthcare, has led to an occupational and public exposure to these nanomaterials. Hence, it becomes a major concern to analyze the issues pertaining to the toxicity of CNTs and find the best suitable ways to counter those challenges. This review summarizes the toxicity issues of CNTs in vitro and in vivo in different organ systems (bio interphases) of the body that result in cellular toxicity.
基金supported by the National Natural Science Foundation of China(Nos.U1804129,21771164,21671205,U1804126)Zhongyuan Youth Talent Support Program of Henan ProvinceZhengzhou University Youth Innovation Program。
文摘Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.
基金Sponsored by the Natural Science Foundation of Heilongjiang Province of China (Grant No.B2007-05)the Natural Scientific Research Innovation Foundation in Harbin Institute of Technology (Grant No.HIT.NSRIF.2009121)
文摘Ionic liquids have been paid much attention and are considered to replace the conventional organic electrolyte and solve the safety issues by virtue of nonvolatility,non-flammability,high ionic conductivity and extended electrochemical steady window.The paper introduces ionic liquids electrolyte on basis of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI),which shows a wide electrochemical window (0.5-4.5 V vs.Li+/Li),and is theoretically feasible as an electrolyte for Li/LiFePO4batteries to improve the safety.Linear sweep voltammetry (LSV) was performed to investigate the electrochemical stability window of the polymer electrolyte.Interfacial resistance for Li/electrolyte/Li symmetric cells and Li/electrolyte/LiFePO4 cells were studied by electrochemical impedance spectroscopy (EIS).The results showed that additive vinylene carbonate (VC) enhances the formation of solid electrolyte interphase film to protect lithium anodes from corrosion and improves the compatibility of ionic liquid electrolyte towards lithium anodes.Accordingly,Li/LiFePO4cells delivers the initial discharge capacity of 124 mAh g-1 at a current rate of 0.1C in the ionic liquid electrolyte (EMITFSI+0.8 mol L-1LiTFSI+5 wt%VC),and shows better cyclability than in the ionic liquid electrolyte without VC.
