Electrolyte additives play an important role in suppressing lithium dendrites through tailoring the composition/property of the SEI,however lacking of additives can achieve high performances both in ether and carbonat...Electrolyte additives play an important role in suppressing lithium dendrites through tailoring the composition/property of the SEI,however lacking of additives can achieve high performances both in ether and carbonate electrolytes hinders further enhancement of the high voltage lithium^-metal batteries.Here,lithium perchlorate(LiClO4)has been presented as an excellent additive to meet the above requirements.An optimized chemical composition of SEI can be achieved through the formation of ionic association.Our results indicate that the LiClO4 behaves like a catalyst,which promotes LiTFSI to form a better SEI to inhibit further reaction.Superior coulombic efficiencies and cycling performances were obtained both in ether and carbonate electrolytes.This study paves a new pathway for designing bi-soluble additives for safe lithium metal batteries.展开更多
The standard association constants of ionic pair [GaCl]2+, Kas, were determined by emf(electromotive force) method at 278.15 to 318.15 K. The thermodynamic quantities for the ionic association process were calculated...The standard association constants of ionic pair [GaCl]2+, Kas, were determined by emf(electromotive force) method at 278.15 to 318.15 K. The thermodynamic quantities for the ionic association process were calculated and it was pointed that the association entropy is driving force to form the ionic pair.展开更多
Gel polymer electrolytes based on the poly （vinylidene fluoride） （PVdF） and the electrolyte of LiClO4 in propylene carbonate （PC） were prepared by the solution casting technique. The ionic conductivity of the ge...Gel polymer electrolytes based on the poly （vinylidene fluoride） （PVdF） and the electrolyte of LiClO4 in propylene carbonate （PC） were prepared by the solution casting technique. The ionic conductivity of the gel electrolytes was above 10^-3 S ·cm^-1 at 30℃ and was affected by the concentration of lithium salt. Because of the strong coulombiq attractions, the dissolved salt ions might aggregate into ion pairs and multiple ion aggregates. The analysis of DSC and X-ray diffraction revealed that the ions association occurred at higher concentration of lithium salt.展开更多
Some ion-associated species existed possibly in NaNO3 solution were investigated via the ab-initio method. The hydrated ion parings, triple and multiple ion clusters in NaNO3 solution are all analogous to those in Mg...Some ion-associated species existed possibly in NaNO3 solution were investigated via the ab-initio method. The hydrated ion parings, triple and multiple ion clusters in NaNO3 solution are all analogous to those in Mg（NO3）2 system except that the bi-dentate structures can not be formed. Only one solvent-shared ion paring has larger v1-NO3^- frequency than the hydrated NO3^- ion. And all triple clusters with two hydrated Na^＋ ions and one NO3^- have larger v1-NO3^- frequency than the hydrated NO3^- ion. The ion association process in NaNO3 solution is predicted as free ions→solvent-separated ion pairings→solvent-shared ion pairings→solvent-shared triple ion clusters→contact triple ion clusters→contact multiple ion clusters→amorphous NaNO3, which is not analogous to that in MgSO4 but those in Mg（NO3）2 and Mg（ClO4）2 systems.展开更多
Introduction Magnesium sulfate is an archetypal 2-2 salt that plays a central role in defining the characteristics of higher valent electrolyte solutions and its solution has been widely used to test various theories...Introduction Magnesium sulfate is an archetypal 2-2 salt that plays a central role in defining the characteristics of higher valent electrolyte solutions and its solution has been widely used to test various theories of strong electrolyte behavior and to develop models of ion association in solution. Up to now, the ion pairs of magnesium sulfate in an aqueous solution have been widely investigated by using different experimental techniques, such as conductometry , cryoscopy potentiometry solubility and Raman spectrometry. However, to our knowledge, no measurement of the standard association constant of the ion pairs, [ MgSO4 ]^0 in a glucosewater mixed solvent is available.展开更多
We present a theoretical investigation of plasma generation in sodium vapor induced by laser radiation tuned to the first resonance line (3S-3P) at λ = 589 ns. A set of rate equations that describe the rate of change...We present a theoretical investigation of plasma generation in sodium vapor induced by laser radiation tuned to the first resonance line (3S-3P) at λ = 589 ns. A set of rate equations that describe the rate of change of the ground and excited states population as well as the temporal variation of the electron energy distribution function (EEDF), beside the formed atomic ion Na+, molecular ion ?and tri-atomic ions are solved numerically. The calculations are carried out at different laser energy and different sodium atomic vapor densities under the experimental conditions of Tapalian and Smith (1993) to test the existence of the formed tri-atomic ions. The numerical calculations of the electron energy distribution function (EEDF) show that a deviation from the Maxwellian distribution due to the super elastic collisions effect. In addition to the competition between associative ionization (3P-3P), associative ionization (3P-3D) and Molnar-Horn- beck ionization processes for producing , the calculations have also shown that the atomic ions Na+ are formed through the Penning ionization and photoionization processes. These results are found to be consistent with the experimental observations.展开更多
The present work reports an investigation on the role played by Na3+ ions formed through triatomic associative ionization collision of Na(4d) atoms with Na2 ground state molecules during the early phase of sodium plas...The present work reports an investigation on the role played by Na3+ ions formed through triatomic associative ionization collision of Na(4d) atoms with Na2 ground state molecules during the early phase of sodium plasma generation by laser ionization based on resonance saturation (LIBORS). Such ionization mechanism is observed experimentally for the first time by Tapalian and Smith (1993) [1]. In their experiment, stepwise atomic excitations are created using two CW dye lasers;one laser is tuned to 589 nm to excite the Na(3s) to Na(3p) D2 transition of sodium and the other laser is tuned 569 nm to excite the Na(3p) to Na(4d) transition. The analysis is grounded on a numerical study of the role of seed electron processes on the temporal evolution of sodium plasma formation by laser irradiation. A previously developed numerical model based on LIBORS technique is modified and adopted. In the present study, the sodium atom is treated as an atom comprises 22 levels namely: a ground state, 18 excited states and three ionic states (atomic, molecular and tri-atomic). The model tackled various collisional and radiative processes that act to enhance and deplete the free electrons generated in the interaction region. The contribution of these processes is signified by solving numerically a system of time-dependent rate equations, which couple the generated atomic and ionic species with the laser fields. Meanwhile, it solves the time-dependent Boltzmann equation for the electron energy distribution function (EEDF) of the generated electrons. The computed values of the EEDF, time evolution of both excited states population and the formed ionic species considering the individual effect of associative ionization, Penning, and photo-ionization and triatomic associative ionization justified the important effect of each of these ionizing processes in creating the early stage electrons. These seed electrons are assumed to rapidly gain energy through superelastic collisions leading eventually to plasma development.展开更多
A spectrophotometric approach for the detection of non-ionic surfactant (Triton X-100) has been proposed in this paper. This method does not involve extraction of the ion-associate with harmful solvents, but employs a...A spectrophotometric approach for the detection of non-ionic surfactant (Triton X-100) has been proposed in this paper. This method does not involve extraction of the ion-associate with harmful solvents, but employs adhesion of the ion-association of potassium/non-ionic surfactants complex and tetraphenylporphyrin tetrasulfonic acid obtained by vigorous shaking. The adhered ion-associate was dissolved with water and its absorbance was measured. The sensitivity for Triton X-100 was determined to be 0.146 (expressed as absorbance of 1 mg/L solution). The adhesion tendency of ion-associate was found to be dependent on the water contact angle, which in turn was influenced by a high adhesion of the ion-associate and by low blank values. In this respect, a tetrafluo-roethylene vessel was found to be the most suitable for the detection of non-ionic surfactants. This spectrophotometrical method is simply and rapidly performed by a procedure based on mechanical shaking and can be employed to detect non-ionic surfactants containing more than 7 polyethylene oxide units.展开更多
Solvation interaction and ion association in solutions of lithium perchlorate/4-methoxymethyl-ethylene carbonate （MEC） have been studied by using Infrared and Raman spectra as a function of concentration of lithium ...Solvation interaction and ion association in solutions of lithium perchlorate/4-methoxymethyl-ethylene carbonate （MEC） have been studied by using Infrared and Raman spectra as a function of concentration of lithium perchlorate. The splitting of ring deformation band and ring ether asymmetric stretching band, and the change of carbonyl stretching band suggest that there should be a strong interaction between Li^＋ and the solvent molecules, and the site of solvation should be the oxygen atom of carbonyl group. The apparent solvation number of Li^＋ was calculated by using band fitting technique. The solvation number was decreased from 3.3 to 1.1 with increasing the concentration of LiClO4/MEC solutions. On the other hand, the band fitting for the ClO4^- band revealed the presence of contact ion pair, and free ClO4^- anion in the concentrated solutions.展开更多
Tertiary amines dissolved in diluents are attractive extractants for recovery of carboxylic acids from dilute aqueous solutions. Quantitative Fourier transform infrared (FTIR) analysis of organic solutions containin...Tertiary amines dissolved in diluents are attractive extractants for recovery of carboxylic acids from dilute aqueous solutions. Quantitative Fourier transform infrared (FTIR) analysis of organic solutions containing various concentrations of trioctylamine (TOA), n octanol, and propionic acid was carried out, and liquid liquid equilibrium was investigated using TOA in n octanol as the solvent. The fraction of ion pair association between TOA and propionic acid in the organic phase was quantitatively determined by FTIR. The apparent reactive extraction equilibrium constant, K 11 , was calculated using the quantitative FTIR spectrum and the equilibrium data. The results show that the fraction of ion pair association depends on diluent concentration, complex dissolution for propionic acid, and association between TOA and propionic acid. The K 11 based on quantitative FTIR has the same loading trend as that from the equilibrium data.展开更多
基金financial supports from the Foundation of National Key Laboratory(No.6142808180202),P.R.Chinathe Pre-Research Foundation(Nos.61407210406,61407210208,41421080401),P.R.China。
文摘Electrolyte additives play an important role in suppressing lithium dendrites through tailoring the composition/property of the SEI,however lacking of additives can achieve high performances both in ether and carbonate electrolytes hinders further enhancement of the high voltage lithium^-metal batteries.Here,lithium perchlorate(LiClO4)has been presented as an excellent additive to meet the above requirements.An optimized chemical composition of SEI can be achieved through the formation of ionic association.Our results indicate that the LiClO4 behaves like a catalyst,which promotes LiTFSI to form a better SEI to inhibit further reaction.Superior coulombic efficiencies and cycling performances were obtained both in ether and carbonate electrolytes.This study paves a new pathway for designing bi-soluble additives for safe lithium metal batteries.
文摘The standard association constants of ionic pair [GaCl]2+, Kas, were determined by emf(electromotive force) method at 278.15 to 318.15 K. The thermodynamic quantities for the ionic association process were calculated and it was pointed that the association entropy is driving force to form the ionic pair.
文摘Gel polymer electrolytes based on the poly （vinylidene fluoride） （PVdF） and the electrolyte of LiClO4 in propylene carbonate （PC） were prepared by the solution casting technique. The ionic conductivity of the gel electrolytes was above 10^-3 S ·cm^-1 at 30℃ and was affected by the concentration of lithium salt. Because of the strong coulombiq attractions, the dissolved salt ions might aggregate into ion pairs and multiple ion aggregates. The analysis of DSC and X-ray diffraction revealed that the ions association occurred at higher concentration of lithium salt.
基金Supported by the National Natural Science Foundation of China(No.20772048)
文摘Some ion-associated species existed possibly in NaNO3 solution were investigated via the ab-initio method. The hydrated ion parings, triple and multiple ion clusters in NaNO3 solution are all analogous to those in Mg（NO3）2 system except that the bi-dentate structures can not be formed. Only one solvent-shared ion paring has larger v1-NO3^- frequency than the hydrated NO3^- ion. And all triple clusters with two hydrated Na^＋ ions and one NO3^- have larger v1-NO3^- frequency than the hydrated NO3^- ion. The ion association process in NaNO3 solution is predicted as free ions→solvent-separated ion pairings→solvent-shared ion pairings→solvent-shared triple ion clusters→contact triple ion clusters→contact multiple ion clusters→amorphous NaNO3, which is not analogous to that in MgSO4 but those in Mg（NO3）2 and Mg（ClO4）2 systems.
文摘Introduction Magnesium sulfate is an archetypal 2-2 salt that plays a central role in defining the characteristics of higher valent electrolyte solutions and its solution has been widely used to test various theories of strong electrolyte behavior and to develop models of ion association in solution. Up to now, the ion pairs of magnesium sulfate in an aqueous solution have been widely investigated by using different experimental techniques, such as conductometry , cryoscopy potentiometry solubility and Raman spectrometry. However, to our knowledge, no measurement of the standard association constant of the ion pairs, [ MgSO4 ]^0 in a glucosewater mixed solvent is available.
文摘We present a theoretical investigation of plasma generation in sodium vapor induced by laser radiation tuned to the first resonance line (3S-3P) at λ = 589 ns. A set of rate equations that describe the rate of change of the ground and excited states population as well as the temporal variation of the electron energy distribution function (EEDF), beside the formed atomic ion Na+, molecular ion ?and tri-atomic ions are solved numerically. The calculations are carried out at different laser energy and different sodium atomic vapor densities under the experimental conditions of Tapalian and Smith (1993) to test the existence of the formed tri-atomic ions. The numerical calculations of the electron energy distribution function (EEDF) show that a deviation from the Maxwellian distribution due to the super elastic collisions effect. In addition to the competition between associative ionization (3P-3P), associative ionization (3P-3D) and Molnar-Horn- beck ionization processes for producing , the calculations have also shown that the atomic ions Na+ are formed through the Penning ionization and photoionization processes. These results are found to be consistent with the experimental observations.
文摘The present work reports an investigation on the role played by Na3+ ions formed through triatomic associative ionization collision of Na(4d) atoms with Na2 ground state molecules during the early phase of sodium plasma generation by laser ionization based on resonance saturation (LIBORS). Such ionization mechanism is observed experimentally for the first time by Tapalian and Smith (1993) [1]. In their experiment, stepwise atomic excitations are created using two CW dye lasers;one laser is tuned to 589 nm to excite the Na(3s) to Na(3p) D2 transition of sodium and the other laser is tuned 569 nm to excite the Na(3p) to Na(4d) transition. The analysis is grounded on a numerical study of the role of seed electron processes on the temporal evolution of sodium plasma formation by laser irradiation. A previously developed numerical model based on LIBORS technique is modified and adopted. In the present study, the sodium atom is treated as an atom comprises 22 levels namely: a ground state, 18 excited states and three ionic states (atomic, molecular and tri-atomic). The model tackled various collisional and radiative processes that act to enhance and deplete the free electrons generated in the interaction region. The contribution of these processes is signified by solving numerically a system of time-dependent rate equations, which couple the generated atomic and ionic species with the laser fields. Meanwhile, it solves the time-dependent Boltzmann equation for the electron energy distribution function (EEDF) of the generated electrons. The computed values of the EEDF, time evolution of both excited states population and the formed ionic species considering the individual effect of associative ionization, Penning, and photo-ionization and triatomic associative ionization justified the important effect of each of these ionizing processes in creating the early stage electrons. These seed electrons are assumed to rapidly gain energy through superelastic collisions leading eventually to plasma development.
文摘A spectrophotometric approach for the detection of non-ionic surfactant (Triton X-100) has been proposed in this paper. This method does not involve extraction of the ion-associate with harmful solvents, but employs adhesion of the ion-association of potassium/non-ionic surfactants complex and tetraphenylporphyrin tetrasulfonic acid obtained by vigorous shaking. The adhered ion-associate was dissolved with water and its absorbance was measured. The sensitivity for Triton X-100 was determined to be 0.146 (expressed as absorbance of 1 mg/L solution). The adhesion tendency of ion-associate was found to be dependent on the water contact angle, which in turn was influenced by a high adhesion of the ion-associate and by low blank values. In this respect, a tetrafluo-roethylene vessel was found to be the most suitable for the detection of non-ionic surfactants. This spectrophotometrical method is simply and rapidly performed by a procedure based on mechanical shaking and can be employed to detect non-ionic surfactants containing more than 7 polyethylene oxide units.
文摘Solvation interaction and ion association in solutions of lithium perchlorate/4-methoxymethyl-ethylene carbonate （MEC） have been studied by using Infrared and Raman spectra as a function of concentration of lithium perchlorate. The splitting of ring deformation band and ring ether asymmetric stretching band, and the change of carbonyl stretching band suggest that there should be a strong interaction between Li^＋ and the solvent molecules, and the site of solvation should be the oxygen atom of carbonyl group. The apparent solvation number of Li^＋ was calculated by using band fitting technique. The solvation number was decreased from 3.3 to 1.1 with increasing the concentration of LiClO4/MEC solutions. On the other hand, the band fitting for the ClO4^- band revealed the presence of contact ion pair, and free ClO4^- anion in the concentrated solutions.
基金the National Natural Science Foundationof China(No. 2 9836 130 )
文摘Tertiary amines dissolved in diluents are attractive extractants for recovery of carboxylic acids from dilute aqueous solutions. Quantitative Fourier transform infrared (FTIR) analysis of organic solutions containing various concentrations of trioctylamine (TOA), n octanol, and propionic acid was carried out, and liquid liquid equilibrium was investigated using TOA in n octanol as the solvent. The fraction of ion pair association between TOA and propionic acid in the organic phase was quantitatively determined by FTIR. The apparent reactive extraction equilibrium constant, K 11 , was calculated using the quantitative FTIR spectrum and the equilibrium data. The results show that the fraction of ion pair association depends on diluent concentration, complex dissolution for propionic acid, and association between TOA and propionic acid. The K 11 based on quantitative FTIR has the same loading trend as that from the equilibrium data.
