Fingerprinting sulfur speciation in aprotic electrolytes is a key to understand fundamental chemistry and design well-performing lithium–sulfur(Li–S)batteries.Lithium polysulfide(LiPS)dissolution and deposition in e...Fingerprinting sulfur speciation in aprotic electrolytes is a key to understand fundamental chemistry and design well-performing lithium–sulfur(Li–S)batteries.Lithium polysulfide(LiPS)dissolution and deposition in ether-based electrolytes during redox reactions have been probed and established by spectroscopy and microscopy.However,detailed LiPS structure and solvation properties influenced by conventional and newly developed electrolytes remain elusive,which exert fundamental challenges and practical difficulties in decoupling battery performance from electrolyte volume.This perspective aims to provide timely information to uncover underlying mechanisms that rein in sulfur speciation by considering the charge density of LiPSs and the coordination strength of solvents/salts.The discussion starts with unlocking the baseline electrolyte formulation to investigate its role in LiPS formation and compatibility.After that,the term coordination strength is used instead of donor number and dielectric constant to describe interactions between solvents and LiPSs and to reveal LiPS structure evolution.This work is expected to encourage the discovery of new electrolyte working mechanisms to develop energy-dense and power-intensive Li–S batteries.展开更多
The oxidation state of sulfur is detected in Na20-CaO-SiO2 float glass by synchrotron radiation X-ray absorption near edge structure （XANES） spectra at the sulfur K edge. The measured spectra show the only presence ...The oxidation state of sulfur is detected in Na20-CaO-SiO2 float glass by synchrotron radiation X-ray absorption near edge structure （XANES） spectra at the sulfur K edge. The measured spectra show the only presence of S^6＋ in the Na20-CaO-SiO2 float glass and the oxidation state of sulfur do not change with the increase of glass depth. It is also found that, after the melt has gone through the molten tin bath, the S^6＋ is the dominant species, but S^2- is also present on both surfaces. It is not certain whether cation bonds to S^2- or not, because there are many cations dissolved in the melted tin which makes the spectrum complicated.展开更多
The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusi...The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue.Herein,we employed in situ/operando X-ray absorption spectroscopy(XAS)to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces,respectively,in a real-time condition.After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix(BSOC),we found the Li/S cell showed greatly improved sulfur utilization and longer life span.The operando S Kedge XAS results revealed that the BSOC modification was bi-functional:trapping polysulfides and catalyzing conversion of sulfur species simultaneously.We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection.Our results could offer potential stratagem for designing more advanced Li/S cells.展开更多
Sulfur K-edge X-ray absorption near-edge structure （XANES） spectroscopy was employed to study the speciation of sulfur in raw coal, ash by-product and fine particulate matter from a small coal-burning boiler. By mea...Sulfur K-edge X-ray absorption near-edge structure （XANES） spectroscopy was employed to study the speciation of sulfur in raw coal, ash by-product and fine particulate matter from a small coal-burning boiler. By means of least square analysis of the XANES spectra, the major organic and inorganic sulfur forms were quantitatively determined. The results show that about 70% of the sulfur in raw coal is present as organic and a minor fraction of the sulfur occurs as other forms： 17% of pyrite and 13% of sulfate. While in bottom ash, fly ash, and PM2.5, the dominant form of sulfur is sulfate, with the percentage of 80,79 and 94, respectively. Moreover, a number of other reduced sulfur including thiophenic sulfur, element sulfur and pyrrhotite are also present. During coal combustion, most of organic sulfur and pyrite were oxidized and released into the atmosphere as SO2 gas, part of them was converted to sulfate existing in coal combustion by-products, and a small part of pyrite was probably reduced to elemental sulfur and pyrrhotite. The results may provide information for assessing the pollution caused by small boiler and developing new methods for the control of SO2 pollution.展开更多
The utilization and speciation transformation of α-S8 and μ-S by the typical mesophilic acidophilic strain Acidithiobacillus ferrooxidans ATCC 23270 were investigated.A.ferrooxidans cells first acclimated to the ene...The utilization and speciation transformation of α-S8 and μ-S by the typical mesophilic acidophilic strain Acidithiobacillus ferrooxidans ATCC 23270 were investigated.A.ferrooxidans cells first acclimated to the energy source α-S8 or μ-S,respectively.The results of cell growth and sulfur oxidation behavior showed that the strain grown on α-S8 entered slowly（about 1 d later） into the exponential phase,while grew faster in the exponential phase and attained higher maximal cell density and lower p H value than that on μ-S.After bio-corrosion,both of the two sulfur samples were evidently eroded and modified by A.ferrooxidans cells.After growth of A.ferrooxidans,the surface composition of amorphous μ-S became 63.1% μ-S and 36.9% α-S8,and that of orthorhombic α-S8 became 68.3% α-S8 and 31.7% μ-S,while the surface compositions of α-S8 and μ-S in sterile experiment were not changed,indicating that these two elemental sulfur species can be interconverted by A.ferrooxidans.展开更多
基金supported by the National Natural Science Foundation of China(grant No.22379121,12275119 and 52227802)Fundamental Research Funds for the Central Universities(grant No.G2022KY0606)+1 种基金Guangdong Grants(grant No.2021ZT09C064)Shenzhen Foundation Research Fund granted by the Shenzhen Science and Technology Innovation Committee(grant No.JCYJ20220530112812028).
文摘Fingerprinting sulfur speciation in aprotic electrolytes is a key to understand fundamental chemistry and design well-performing lithium–sulfur(Li–S)batteries.Lithium polysulfide(LiPS)dissolution and deposition in ether-based electrolytes during redox reactions have been probed and established by spectroscopy and microscopy.However,detailed LiPS structure and solvation properties influenced by conventional and newly developed electrolytes remain elusive,which exert fundamental challenges and practical difficulties in decoupling battery performance from electrolyte volume.This perspective aims to provide timely information to uncover underlying mechanisms that rein in sulfur speciation by considering the charge density of LiPSs and the coordination strength of solvents/salts.The discussion starts with unlocking the baseline electrolyte formulation to investigate its role in LiPS formation and compatibility.After that,the term coordination strength is used instead of donor number and dielectric constant to describe interactions between solvents and LiPSs and to reveal LiPS structure evolution.This work is expected to encourage the discovery of new electrolyte working mechanisms to develop energy-dense and power-intensive Li–S batteries.
基金Funded by the National Natural Science Foundation of China(No.50972136)
文摘The oxidation state of sulfur is detected in Na20-CaO-SiO2 float glass by synchrotron radiation X-ray absorption near edge structure （XANES） spectra at the sulfur K edge. The measured spectra show the only presence of S^6＋ in the Na20-CaO-SiO2 float glass and the oxidation state of sulfur do not change with the increase of glass depth. It is also found that, after the melt has gone through the molten tin bath, the S^6＋ is the dominant species, but S^2- is also present on both surfaces. It is not certain whether cation bonds to S^2- or not, because there are many cations dissolved in the melted tin which makes the spectrum complicated.
基金financially supported by the National Key R&D Program of China(2016YFB0100100)the National Natural Science Foundation of China(Nos.21433013,U1832218)the support from China Scholarship Council
文摘The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur(Li/S)cells.A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue.Herein,we employed in situ/operando X-ray absorption spectroscopy(XAS)to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces,respectively,in a real-time condition.After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix(BSOC),we found the Li/S cell showed greatly improved sulfur utilization and longer life span.The operando S Kedge XAS results revealed that the BSOC modification was bi-functional:trapping polysulfides and catalyzing conversion of sulfur species simultaneously.We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection.Our results could offer potential stratagem for designing more advanced Li/S cells.
基金Supported by Major Project of Knowledge Innovation Program of Chinese Academy of Sciences (KJCX3.SYW.N3)Exploration Project of Knowledge Innovation Program of Chinese Academy of Sciences (90070301)+1 种基金National Natural Science Foundation of China (10775174, 10775150)BEPC National Laboratory (Vr-07113)
文摘Sulfur K-edge X-ray absorption near-edge structure （XANES） spectroscopy was employed to study the speciation of sulfur in raw coal, ash by-product and fine particulate matter from a small coal-burning boiler. By means of least square analysis of the XANES spectra, the major organic and inorganic sulfur forms were quantitatively determined. The results show that about 70% of the sulfur in raw coal is present as organic and a minor fraction of the sulfur occurs as other forms： 17% of pyrite and 13% of sulfate. While in bottom ash, fly ash, and PM2.5, the dominant form of sulfur is sulfate, with the percentage of 80,79 and 94, respectively. Moreover, a number of other reduced sulfur including thiophenic sulfur, element sulfur and pyrrhotite are also present. During coal combustion, most of organic sulfur and pyrite were oxidized and released into the atmosphere as SO2 gas, part of them was converted to sulfate existing in coal combustion by-products, and a small part of pyrite was probably reduced to elemental sulfur and pyrrhotite. The results may provide information for assessing the pollution caused by small boiler and developing new methods for the control of SO2 pollution.
基金Project(51274257)supported by the National Natural Science Foundation of ChinaProject(U1232103)supported by the Joint Funds of National Natural Science Foundation of China and Large Scientific Facility Foundation of Chinese Academy of SciencesProject(VR-12419)supported by the Beijing Synchrotron Radiation Facility Public User Program
文摘The utilization and speciation transformation of α-S8 and μ-S by the typical mesophilic acidophilic strain Acidithiobacillus ferrooxidans ATCC 23270 were investigated.A.ferrooxidans cells first acclimated to the energy source α-S8 or μ-S,respectively.The results of cell growth and sulfur oxidation behavior showed that the strain grown on α-S8 entered slowly（about 1 d later） into the exponential phase,while grew faster in the exponential phase and attained higher maximal cell density and lower p H value than that on μ-S.After bio-corrosion,both of the two sulfur samples were evidently eroded and modified by A.ferrooxidans cells.After growth of A.ferrooxidans,the surface composition of amorphous μ-S became 63.1% μ-S and 36.9% α-S8,and that of orthorhombic α-S8 became 68.3% α-S8 and 31.7% μ-S,while the surface compositions of α-S8 and μ-S in sterile experiment were not changed,indicating that these two elemental sulfur species can be interconverted by A.ferrooxidans.
