The electrolyte version of SRK plus association equation of state(e SRK-CPA Eo S) was employed to correlate CO2 solubility in MDEA aqueous solutions. The applied model comprises the classic form of CPA Eo S including ...The electrolyte version of SRK plus association equation of state(e SRK-CPA Eo S) was employed to correlate CO2 solubility in MDEA aqueous solutions. The applied model comprises the classic form of CPA Eo S including SRK Eo S plus Wertheim association term in addition to MSA theory and Born terms so that the two last terms are responsible for the long-range interactions. A reaction-containing bubble pressure computation technique comprising two nested loops was utilized to model the systems. The internal loop, calculates the liquid phase concentrations via reaction, mass and charge balance equation solving, whereas, the vapor phase concentrations will be obtained in the external one. 470 experimental data were used to correlate binary subsystems and the H2O + MDEA + CO2 ternary system. Since, there not exist any binary VLE data for MDEA + CO2 subsystem, two fitting scenarios were applied. At the first scenario, the binary interaction parameter was assumed equal to zero, while, in second approach the parameter was obtained through ternary system correlation. Both scenarios show very good accuracy in that the Absolute Average Deviation percentages(AAD) obtained were 19.12% and 18.85%, respectively. Also, to show the efficiency of the used model, a comparison between our results and those of the best-known models was made.Finally, having model parameters for H2S solubility from our previous work [A. Afsharpour, Petroleum Science and Technology 35(3)(2017) 292-298], simultaneous solubility of CO2+ H2S mixtures in MDEA solutions was predicted using the e SRK-CPA Eo S with no new optimizable parameters. As the results show,the applied model has a good performance for correlation and prediction of acid gas solubility in a wide range of pressures, temperatures, acid gas loadings, and MDEA concentrations.展开更多
A new equation of state(PHSMSA EOS)based on perturbation theory is developed for calculating high-pressure phase equilibria of aqueous electrolyte systems containing supercritical gases,light hydrocarbons andpolar com...A new equation of state(PHSMSA EOS)based on perturbation theory is developed for calculating high-pressure phase equilibria of aqueous electrolyte systems containing supercritical gases,light hydrocarbons andpolar components.The binary interaction parameters are determined:for ion-ion pairs by regression of ionicactivity coefficient data;for molecule-molecule pairs by fitting the VLE data of binary nonelectrolyte mixtures;and for ion-molecule pairs by fitting the gas solubility data of ternary gas-water-salt systems.The new EOShas been tested on the prediction of solubilities of methane,nitrogen and natural gas mixtures in brine.Sat-isfactory agreement with the experimental data measured by authors and other investigators is observed.展开更多
In this study, an organic electrolyte solution based on zinc acetate/diethylene glycol(ZA/DEG) is introduced for the selective purification of cyclotetramethylene tetranitramine(HMX) high explosive from its identical ...In this study, an organic electrolyte solution based on zinc acetate/diethylene glycol(ZA/DEG) is introduced for the selective purification of cyclotetramethylene tetranitramine(HMX) high explosive from its identical homologue cyclotrimethylene trinitramine(RDX). The dielectric constant of various organic solutions were investigated through Electrochemical Impedance Spectroscopy(EIS) in the range of 1.0 Hz—30 MHz. and some quantum-chemical descriptors of RDX and HMX dissolutions in the ZA cosolvent were analyzed using Density Functional Theory(DFT). The results show dielectric constant and solubility of RDX is higher than that of HMX, and by increasing of ZA concentration in DEG solvent, the values of dielectric constants were enhanced. Furthermore, the presence of ZA cosolvent on the solubility of two explosives was statistically investigated by Central Composite Design(CCD) of experiment, and some solubility parameters including activity coefficient, dissolving enthalpy, and mixing enthalpies were determined. The experimental results indicate that the weight ratio of RDX to HMX solubility in the proposed organic electrolyte changes up to 30 times, which provides a selective and sequential separation method to separate two materials with similar chemical properties with a separation efficiency>98% and HMX purity> 99.8%. The X-Ray Diffraction(XRD) analysis, High-Performance Liquid Chromatography(HPLC), Laser-Induced Breakdown Spectroscopy(LIBS), and Fourier Transform Infrared Spectroscopy(FT-IR) approves the acceptable quality of the separated materials. The proposed method makes the efficient and safe purification of high-quality HMX for application in oil and gas well perforating gun charges, using a nonvolatile and inflammable organic electrolyte.展开更多
Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is...Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is proposed by using molecular dynamics simulation,and the relationship between ion-to-ion interaction and salt solubility in a simulated seawater water-salt system is investigated.By analyzing the variation of distance and contact time between ions in an electrolyte solution,from both spatial and temporal perspectives,new parameters were proposed to describe the interaction between ions:interaction distance(ID),and interaction time ratio(ITR).The best correlation between characteristic time ratio and solubility was found for a molar ratio of salt-to-water of 10:100 with a correlation coefficient of 0.96.For the same salt,a positive correlation was found between CTR and the molar ratio of salt and water.For type 1-1,type 2-1,type 1-2,and type 2-2 salts,the correlation coefficients between CTR and solubility were 0.93,0.96,0.92,and 0.98 for a salt-to-water molar ratio of 10:100,respectively.The solubility of multiple salts was predicted by simulations and compared with experimental values,yielding an average relative deviation of 12.4%.The new ion-interaction parameters offer significant advantages in describing strongly correlated and strongly hydrated electrolyte solutions.展开更多
The chemical reaction and dissolution processes of RE2 O3 in REF3-LiF（RE = La and Nd） molten salts were studied by X-ray diffraction, differential thermal analysis and chemical analysis. Firstly, RE2 O3 disperses in...The chemical reaction and dissolution processes of RE2 O3 in REF3-LiF（RE = La and Nd） molten salts were studied by X-ray diffraction, differential thermal analysis and chemical analysis. Firstly, RE2 O3 disperses in molten salts and reacts with REF3 and LiF, which lead to the generation of a new phase REOF, resulting in the dissociation or formation of complex ions by part of REOF, and the sedimentation of excessive REOF at the bottom. The RE contents in molten salts were used to determine the solubility of RE2 O3. The results show that with 20 mol%-40 mol% of REF3, the solubility ranges from 1.79 to 3.05 g RE2 O3 per100 g electrolyte and the corresponding mole concentration is 0.33%-0.87%. RE2 O3 solubility increases with increasing temperature and REF3 concentration. The natural logarithm of the RE2 O3 solubility is plotted against 1/T and can be interpreted by linear relationship. The fitting parameters can be used to estimate the solubility of RE2 O3 with minimized experimental efforts and difficult experiment conditions.展开更多
1-butyl-3-methylimidazolium perchlorate([BMIM]ClO4) was synthesized by two steps with N-methylimidazolium.Some physico-chemical properties,such as density,surface tension,viscosity,electrical conductivity as well as e...1-butyl-3-methylimidazolium perchlorate([BMIM]ClO4) was synthesized by two steps with N-methylimidazolium.Some physico-chemical properties,such as density,surface tension,viscosity,electrical conductivity as well as electrochemical window,were investigated and solvent performance was also studied.The results show that this kind of ionic liquid is an excellent electrolyte with low viscosity,high electrical conductivity and wide electrochemical window.In addition,[BMIM]ClO4 is soluble in most conventional solvents and some metal oxides have high solubility in it,which lays the foundation of direct electrolysis of metal oxides in this ionic liquid.展开更多
Porous carbon has been applied for lithium-sulfur battery cathodes,and carbonized metal-organic framework(MOF)is advantageous in tuning the morphology.Herein,we have systematically synthesized water-distorted MOF(WDM)...Porous carbon has been applied for lithium-sulfur battery cathodes,and carbonized metal-organic framework(MOF)is advantageous in tuning the morphology.Herein,we have systematically synthesized water-distorted MOF(WDM)derived porous carbon via controlling the proportion of both water in a mixed solvent(dimethylformamide and water)and ligand in MOF-5 precursors(metal and ligand),which is categorized by its morphology(i.e.Cracked stone(closed),Tassel(open)and Intermediate(semi-open)).For example,decrease in water and increase in ligand content induce Cracked stone WDMs which showed the highest specific surface area(2742-2990 m^(2)/g)and pore volume(2.81-3.28 cm^(3)/g)after carbonization.Morphological effect of carbonized WDMs(CWDMs)on battery performance was examined by introducing electrolytes with different sulfur reduction mechanisms(i.e.DOL/DME and ACN_(2) LiTFSITTE):Closed framework effectively confines polysulfide,whereas open framework enhances electrolyte accessibility.The initial capacities of the batteries were in the following order:Cracked stone>Intermediate>Tassel for DOL/DME and Intermediate>Tassel>Cracked stone for ACN_(2) LiTFSI-TTE.To note,Intermediate CWDM exhibited the highest initial capacity and retained capacity after 100 cycles(1398 and 747 mAh/g)in ACN_(2) LiTFSI-TTE electrolyte having advantages from both open and closed frameworks.In sum,we could correlate cathode morphology(openness and pore structure)and electrolyte type(i.e.polysulfide solubility)with lithium-sulfur battery performance.展开更多
The alumina solubility in the title system within the composition range of KR{m（K3AlF6）/[m（K3AlF6）＋ m（Na3AlF6）]} 10%―50%, a ternary Na3AlF6-K3AlF6-AlF3 molten system with 23%―29%（mass fraction） AlF3 was inv...The alumina solubility in the title system within the composition range of KR{m（K3AlF6）/[m（K3AlF6）＋ m（Na3AlF6）]} 10%―50%, a ternary Na3AlF6-K3AlF6-AlF3 molten system with 23%―29%（mass fraction） AlF3 was investigated by measuring the mass loss of a rotating sintered corundum disc. And the following empirical equation was derived when superheat degree was no more than 60 °C： w（Al2O3）sat=A×（T/1000）B, where A= –1.85774＋ 26.754234w（AlF3）–0.3683–0.00783KR2.363＋0.010266KR2.3048＋0.7902w（AlF3）0.00652, B=112.4625–53.2567w（AlF3）0.4236＋ 5.1079w（AlF3）0.9241＋0.01542w（AlF3）1.3540. Considering both higher alumina solubility and not too high superheat de gree are required, alumina solubility of different compositions at not the same temperature but the same superheat degree was studied, which will be more industrial helpful for selecting prospective compositions. The results show that the composition deserved to be further tested in lower temperature cells is 10%―30% KR and 23%―26%（mass fraction） AlF3.展开更多
A two parameters equation of state (EOS) for nonaqueous electrolyte solutions system has been developed. The equation is in terms of Helmholtz free energy and incorporated with results of low density expansion of non-...A two parameters equation of state (EOS) for nonaqueous electrolyte solutions system has been developed. The equation is in terms of Helmholtz free energy and incorporated with results of low density expansion of non-primitive mean spherical approximation. The EOS was tested for experimental data reported in literatures of 9 nonaqueous single electrolyte solutions of which the temperature was 298.15 K, and it also has a good predictive capability for nonaqueous electrolyte solutions at different temperature in this work. The comparisons with EOSs published earlier by other researchers in literatures are carried out in detail.展开更多
The lithium-sulfur(Li-S)technology is the most promising candidate for next-generation batteries due to its high theoretical specific energy and steady progress for applications requiring lightweight batteries such as...The lithium-sulfur(Li-S)technology is the most promising candidate for next-generation batteries due to its high theoretical specific energy and steady progress for applications requiring lightweight batteries such as aviation or heavy electric vehicles.For these applications,however,the rate capability of Li-S cells requires significant improvement.Advanced electrolyte formulations in Li-S batteries enable new pathways for cell development and adjustment of all components.However,their rate capability at pouch cell level is often neither evaluated nor compared to state of the art(SOTA)LiTFSI/dimethoxyethane/dioxolane(LITFSI:lithium-bis(trifluoromethylsulfonyl)imide)electrolyte.Herein,the combination of the sparingly polysulfide(PS)solvating hexylmethylether/1,2-dimethoxyethane(HME/DME)electrolyte and highly conductive carbon nanotube Buckypaper(CNT-BP)with low porosity was evaluated in both coin and pouch cells and compared to dimethoxyethane/dioxolane reference electrolyte.An advanced sulfur transfer melt infiltration was employed for cathode production with CNT-BP.The Li+ion coordination in the HME/DME electrolyte was investigated by nuclear magnetic resonance(NMR)and Raman spectroscopy.Additionally,ionic conductivity and viscosity was investigated for the pristine electrolyte and a polysulfide-statured solution.Both electrolytes,DME/DOL-1/1(DOL:1,3-dioxolane)and HME/DME-8/2,are then combined with CNT-BP and transferred to multi-layered pouch cells.This study reveals that the ionic conductivity of the electrolyte increases drastically over state of(dis)charge especially for DME/DOL electrolyte and lean electrolyte regime leading to a better rate capability for the sparingly polysulfide solvating electrolyte.The evaluation in prototype cells is an important step towards bespoke adaption of Li-S batteries for practical applications.展开更多
This paper reports an investigation into the characterisation of liquidaivapor electrolyte solutions at high pressure and high temperature. A procedure to enable calcuIations of methane, carbon dioxide and hydrogen su...This paper reports an investigation into the characterisation of liquidaivapor electrolyte solutions at high pressure and high temperature. A procedure to enable calcuIations of methane, carbon dioxide and hydrogen sulphide solubilities in brines (0-6 m.) for temperature from 25 to 350℃ and for pressures from 1 to 1800 bar is presented. The model is based on Helgeson, Kirkham and Flowers modified equations of state (HKF) and on the semi-empirical interaction model introduced by Pitzer. HKF modified equations of state are used to calculate the reference fugacity of gas species, and the Pitzer ionic interaction model is used to calculate the activity coefficient of dissolved species (i.e. ionic or neutral).The efficiency of the combination of the two models is confirmed by several comparisons with data in the literature.展开更多
This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,u...This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,under suitable conditions,the NH_(4)^(+)and Mn^(2+)contents in EMR decrease notably with the increasing CS content,accompanied by an increase in pH value.Furthermore,the concentration of NH_(4)^(+)in EMR considerably decreases with the increasing liquid-to-solid ratio,eventually stabilizing.Similarly,the pH value first increases and then decreases,ultimately stabilizing.At a CS content of 12%and a liquid-to-solid ratio of 0.7,the leaching concentrations of NH_(4)^(+)and Mn^(2+)in EMR(127.7 mg/kg and 0.15 mg/L,respectively)fall below the standard detection limit(2 mg/L),with the pH measuring 8.26,meeting the conditions outlined in the GB 8978.NH_(4)^(+)is converted to NH_(3),while Mn^(2+)is transformed into solid precipitates such as Mn(OH)_(2),Mn_(2)O_(3),MnO_(2),Ca_(3)Mn_(2)O_(7),and Ca_(2)MnO_(4).The majority of manganese ions exist in trivalent or tetravalent states and remain stable over time.The cost of using CS as a reagent for treating 1 ton of EMR is merely$1.01.The high OH^(-)concentration provided by CS enables the effective removal of NH_(4)^(+)from EMR and the solidification of Mn^(2+)during thermal reactions.展开更多
Zinc （Zn） is essential to plant growth and relatively mobile in soils. This study was conducted to assess the effect of common ions （Ca2＋, K＋, Na＋, NH＋, CI-, NO3-, and H2PO4） on sorption of Zn in surface sampl...Zinc （Zn） is essential to plant growth and relatively mobile in soils. This study was conducted to assess the effect of common ions （Ca2＋, K＋, Na＋, NH＋, CI-, NO3-, and H2PO4） on sorption of Zn in surface samples of ten calcareous soils from western Iran using 10 mmol L-1 KC1, KNO3, KH2P04, Ca（N03）2, NAN03, and NH4N03 solutions as background electrolytes. The results indicated that both NH＋, K＋, and Ca2＋ equally decreased Zn sorption as compared to Na＋. Zinc sorption was decreased by H2PO4- as compared to NO3 and Cl-. The Langmuir and Freundlich equations fitted closely to the sorption data of all ions. The Langmuir maximum, bonding energy constant, and Freundlich distribution coefficient for Zn sorption differed among the various ionic background electrolytes. Langmuir sorption parameters showed that the presence of H2PO4- decreased the maximum Zn adsorbed, but increased the bonding energy. Although K＋ and NH＋ equally influenced maximum Zn adsorbed, they differed in their effect on the distribution coefficient of Zn in soils. Values of saturation index calculated using Visual MINTEQ indicated that at the low Zn concentration, Zn solubility was controlled by sorption reactions and at the high Zn concentration, it was mainly controlled by sorption and mineral precipitation reactions, such as precipitation of Zn3（PO4）2.4H2O, Zn5（OH）6（CO3）2, and ZnCO3. For most ionic background electrolytes, soil pH, CaC03, and cation exchange capacity （CEC） were significantly correlated with sorption parameters.展开更多
A new thermodynamic model derived from a Helmholtz energy function is established by considering the contribution of various particle interactions in the electrolyte solutions to calculate the solubility of gases in a...A new thermodynamic model derived from a Helmholtz energy function is established by considering the contribution of various particle interactions in the electrolyte solutions to calculate the solubility of gases in aqueous electrolytes. A good agreement between the experimental data and calculation results is obtained. Meanwhile, the results show that this model is superior to the MPT EOS under elevated pressure.展开更多
文摘The electrolyte version of SRK plus association equation of state(e SRK-CPA Eo S) was employed to correlate CO2 solubility in MDEA aqueous solutions. The applied model comprises the classic form of CPA Eo S including SRK Eo S plus Wertheim association term in addition to MSA theory and Born terms so that the two last terms are responsible for the long-range interactions. A reaction-containing bubble pressure computation technique comprising two nested loops was utilized to model the systems. The internal loop, calculates the liquid phase concentrations via reaction, mass and charge balance equation solving, whereas, the vapor phase concentrations will be obtained in the external one. 470 experimental data were used to correlate binary subsystems and the H2O + MDEA + CO2 ternary system. Since, there not exist any binary VLE data for MDEA + CO2 subsystem, two fitting scenarios were applied. At the first scenario, the binary interaction parameter was assumed equal to zero, while, in second approach the parameter was obtained through ternary system correlation. Both scenarios show very good accuracy in that the Absolute Average Deviation percentages(AAD) obtained were 19.12% and 18.85%, respectively. Also, to show the efficiency of the used model, a comparison between our results and those of the best-known models was made.Finally, having model parameters for H2S solubility from our previous work [A. Afsharpour, Petroleum Science and Technology 35(3)(2017) 292-298], simultaneous solubility of CO2+ H2S mixtures in MDEA solutions was predicted using the e SRK-CPA Eo S with no new optimizable parameters. As the results show,the applied model has a good performance for correlation and prediction of acid gas solubility in a wide range of pressures, temperatures, acid gas loadings, and MDEA concentrations.
文摘A new equation of state(PHSMSA EOS)based on perturbation theory is developed for calculating high-pressure phase equilibria of aqueous electrolyte systems containing supercritical gases,light hydrocarbons andpolar components.The binary interaction parameters are determined:for ion-ion pairs by regression of ionicactivity coefficient data;for molecule-molecule pairs by fitting the VLE data of binary nonelectrolyte mixtures;and for ion-molecule pairs by fitting the gas solubility data of ternary gas-water-salt systems.The new EOShas been tested on the prediction of solubilities of methane,nitrogen and natural gas mixtures in brine.Sat-isfactory agreement with the experimental data measured by authors and other investigators is observed.
基金financial support of this work by Malek-ashtar University of Technology (I.R. Iran)。
文摘In this study, an organic electrolyte solution based on zinc acetate/diethylene glycol(ZA/DEG) is introduced for the selective purification of cyclotetramethylene tetranitramine(HMX) high explosive from its identical homologue cyclotrimethylene trinitramine(RDX). The dielectric constant of various organic solutions were investigated through Electrochemical Impedance Spectroscopy(EIS) in the range of 1.0 Hz—30 MHz. and some quantum-chemical descriptors of RDX and HMX dissolutions in the ZA cosolvent were analyzed using Density Functional Theory(DFT). The results show dielectric constant and solubility of RDX is higher than that of HMX, and by increasing of ZA concentration in DEG solvent, the values of dielectric constants were enhanced. Furthermore, the presence of ZA cosolvent on the solubility of two explosives was statistically investigated by Central Composite Design(CCD) of experiment, and some solubility parameters including activity coefficient, dissolving enthalpy, and mixing enthalpies were determined. The experimental results indicate that the weight ratio of RDX to HMX solubility in the proposed organic electrolyte changes up to 30 times, which provides a selective and sequential separation method to separate two materials with similar chemical properties with a separation efficiency>98% and HMX purity> 99.8%. The X-Ray Diffraction(XRD) analysis, High-Performance Liquid Chromatography(HPLC), Laser-Induced Breakdown Spectroscopy(LIBS), and Fourier Transform Infrared Spectroscopy(FT-IR) approves the acceptable quality of the separated materials. The proposed method makes the efficient and safe purification of high-quality HMX for application in oil and gas well perforating gun charges, using a nonvolatile and inflammable organic electrolyte.
基金supported by the National Natural Science Foundation of China(No.21776264).
文摘Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is proposed by using molecular dynamics simulation,and the relationship between ion-to-ion interaction and salt solubility in a simulated seawater water-salt system is investigated.By analyzing the variation of distance and contact time between ions in an electrolyte solution,from both spatial and temporal perspectives,new parameters were proposed to describe the interaction between ions:interaction distance(ID),and interaction time ratio(ITR).The best correlation between characteristic time ratio and solubility was found for a molar ratio of salt-to-water of 10:100 with a correlation coefficient of 0.96.For the same salt,a positive correlation was found between CTR and the molar ratio of salt and water.For type 1-1,type 2-1,type 1-2,and type 2-2 salts,the correlation coefficients between CTR and solubility were 0.93,0.96,0.92,and 0.98 for a salt-to-water molar ratio of 10:100,respectively.The solubility of multiple salts was predicted by simulations and compared with experimental values,yielding an average relative deviation of 12.4%.The new ion-interaction parameters offer significant advantages in describing strongly correlated and strongly hydrated electrolyte solutions.
基金supported by the National High Technology Research and Development Program(2011AA03A409)Fundamental Research Funds for the Central Universities(N110202002)
文摘The chemical reaction and dissolution processes of RE2 O3 in REF3-LiF（RE = La and Nd） molten salts were studied by X-ray diffraction, differential thermal analysis and chemical analysis. Firstly, RE2 O3 disperses in molten salts and reacts with REF3 and LiF, which lead to the generation of a new phase REOF, resulting in the dissociation or formation of complex ions by part of REOF, and the sedimentation of excessive REOF at the bottom. The RE contents in molten salts were used to determine the solubility of RE2 O3. The results show that with 20 mol%-40 mol% of REF3, the solubility ranges from 1.79 to 3.05 g RE2 O3 per100 g electrolyte and the corresponding mole concentration is 0.33%-0.87%. RE2 O3 solubility increases with increasing temperature and REF3 concentration. The natural logarithm of the RE2 O3 solubility is plotted against 1/T and can be interpreted by linear relationship. The fitting parameters can be used to estimate the solubility of RE2 O3 with minimized experimental efforts and difficult experiment conditions.
基金Project(50574031) supported by the National Natural Science Foundation of China
文摘1-butyl-3-methylimidazolium perchlorate([BMIM]ClO4) was synthesized by two steps with N-methylimidazolium.Some physico-chemical properties,such as density,surface tension,viscosity,electrical conductivity as well as electrochemical window,were investigated and solvent performance was also studied.The results show that this kind of ionic liquid is an excellent electrolyte with low viscosity,high electrical conductivity and wide electrochemical window.In addition,[BMIM]ClO4 is soluble in most conventional solvents and some metal oxides have high solubility in it,which lays the foundation of direct electrolysis of metal oxides in this ionic liquid.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea by the Korea government(MEST)(grant number NRF2019R1A2C4069922)the“LG Research Fund for New Faculty”by LG Chem。
文摘Porous carbon has been applied for lithium-sulfur battery cathodes,and carbonized metal-organic framework(MOF)is advantageous in tuning the morphology.Herein,we have systematically synthesized water-distorted MOF(WDM)derived porous carbon via controlling the proportion of both water in a mixed solvent(dimethylformamide and water)and ligand in MOF-5 precursors(metal and ligand),which is categorized by its morphology(i.e.Cracked stone(closed),Tassel(open)and Intermediate(semi-open)).For example,decrease in water and increase in ligand content induce Cracked stone WDMs which showed the highest specific surface area(2742-2990 m^(2)/g)and pore volume(2.81-3.28 cm^(3)/g)after carbonization.Morphological effect of carbonized WDMs(CWDMs)on battery performance was examined by introducing electrolytes with different sulfur reduction mechanisms(i.e.DOL/DME and ACN_(2) LiTFSITTE):Closed framework effectively confines polysulfide,whereas open framework enhances electrolyte accessibility.The initial capacities of the batteries were in the following order:Cracked stone>Intermediate>Tassel for DOL/DME and Intermediate>Tassel>Cracked stone for ACN_(2) LiTFSI-TTE.To note,Intermediate CWDM exhibited the highest initial capacity and retained capacity after 100 cycles(1398 and 747 mAh/g)in ACN_(2) LiTFSI-TTE electrolyte having advantages from both open and closed frameworks.In sum,we could correlate cathode morphology(openness and pore structure)and electrolyte type(i.e.polysulfide solubility)with lithium-sulfur battery performance.
基金Supported by the National Basic Research Program of China(No.2005CB623703)the National High-Tech Research and Development Program of China(No.2008AA030503)
文摘The alumina solubility in the title system within the composition range of KR{m（K3AlF6）/[m（K3AlF6）＋ m（Na3AlF6）]} 10%―50%, a ternary Na3AlF6-K3AlF6-AlF3 molten system with 23%―29%（mass fraction） AlF3 was investigated by measuring the mass loss of a rotating sintered corundum disc. And the following empirical equation was derived when superheat degree was no more than 60 °C： w（Al2O3）sat=A×（T/1000）B, where A= –1.85774＋ 26.754234w（AlF3）–0.3683–0.00783KR2.363＋0.010266KR2.3048＋0.7902w（AlF3）0.00652, B=112.4625–53.2567w（AlF3）0.4236＋ 5.1079w（AlF3）0.9241＋0.01542w（AlF3）1.3540. Considering both higher alumina solubility and not too high superheat de gree are required, alumina solubility of different compositions at not the same temperature but the same superheat degree was studied, which will be more industrial helpful for selecting prospective compositions. The results show that the composition deserved to be further tested in lower temperature cells is 10%―30% KR and 23%―26%（mass fraction） AlF3.
文摘A two parameters equation of state (EOS) for nonaqueous electrolyte solutions system has been developed. The equation is in terms of Helmholtz free energy and incorporated with results of low density expansion of non-primitive mean spherical approximation. The EOS was tested for experimental data reported in literatures of 9 nonaqueous single electrolyte solutions of which the temperature was 298.15 K, and it also has a good predictive capability for nonaqueous electrolyte solutions at different temperature in this work. The comparisons with EOSs published earlier by other researchers in literatures are carried out in detail.
基金financed by the German Ministry of Education and Research(BMBF)in the project“HiPoLiS”(No.03XP0178A).
文摘The lithium-sulfur(Li-S)technology is the most promising candidate for next-generation batteries due to its high theoretical specific energy and steady progress for applications requiring lightweight batteries such as aviation or heavy electric vehicles.For these applications,however,the rate capability of Li-S cells requires significant improvement.Advanced electrolyte formulations in Li-S batteries enable new pathways for cell development and adjustment of all components.However,their rate capability at pouch cell level is often neither evaluated nor compared to state of the art(SOTA)LiTFSI/dimethoxyethane/dioxolane(LITFSI:lithium-bis(trifluoromethylsulfonyl)imide)electrolyte.Herein,the combination of the sparingly polysulfide(PS)solvating hexylmethylether/1,2-dimethoxyethane(HME/DME)electrolyte and highly conductive carbon nanotube Buckypaper(CNT-BP)with low porosity was evaluated in both coin and pouch cells and compared to dimethoxyethane/dioxolane reference electrolyte.An advanced sulfur transfer melt infiltration was employed for cathode production with CNT-BP.The Li+ion coordination in the HME/DME electrolyte was investigated by nuclear magnetic resonance(NMR)and Raman spectroscopy.Additionally,ionic conductivity and viscosity was investigated for the pristine electrolyte and a polysulfide-statured solution.Both electrolytes,DME/DOL-1/1(DOL:1,3-dioxolane)and HME/DME-8/2,are then combined with CNT-BP and transferred to multi-layered pouch cells.This study reveals that the ionic conductivity of the electrolyte increases drastically over state of(dis)charge especially for DME/DOL electrolyte and lean electrolyte regime leading to a better rate capability for the sparingly polysulfide solvating electrolyte.The evaluation in prototype cells is an important step towards bespoke adaption of Li-S batteries for practical applications.
文摘This paper reports an investigation into the characterisation of liquidaivapor electrolyte solutions at high pressure and high temperature. A procedure to enable calcuIations of methane, carbon dioxide and hydrogen sulphide solubilities in brines (0-6 m.) for temperature from 25 to 350℃ and for pressures from 1 to 1800 bar is presented. The model is based on Helgeson, Kirkham and Flowers modified equations of state (HKF) and on the semi-empirical interaction model introduced by Pitzer. HKF modified equations of state are used to calculate the reference fugacity of gas species, and the Pitzer ionic interaction model is used to calculate the activity coefficient of dissolved species (i.e. ionic or neutral).The efficiency of the combination of the two models is confirmed by several comparisons with data in the literature.
基金Funded by the Guangxi Key Research and Development Program(Guike AB23026071 and Guike AB24010020)the Guangxi Science and Technology Base and Talent Project(Guike AD24010062)the Guangxi Beibu Gulf Engineering Research Center for Green Marine Materials。
文摘This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,under suitable conditions,the NH_(4)^(+)and Mn^(2+)contents in EMR decrease notably with the increasing CS content,accompanied by an increase in pH value.Furthermore,the concentration of NH_(4)^(+)in EMR considerably decreases with the increasing liquid-to-solid ratio,eventually stabilizing.Similarly,the pH value first increases and then decreases,ultimately stabilizing.At a CS content of 12%and a liquid-to-solid ratio of 0.7,the leaching concentrations of NH_(4)^(+)and Mn^(2+)in EMR(127.7 mg/kg and 0.15 mg/L,respectively)fall below the standard detection limit(2 mg/L),with the pH measuring 8.26,meeting the conditions outlined in the GB 8978.NH_(4)^(+)is converted to NH_(3),while Mn^(2+)is transformed into solid precipitates such as Mn(OH)_(2),Mn_(2)O_(3),MnO_(2),Ca_(3)Mn_(2)O_(7),and Ca_(2)MnO_(4).The majority of manganese ions exist in trivalent or tetravalent states and remain stable over time.The cost of using CS as a reagent for treating 1 ton of EMR is merely$1.01.The high OH^(-)concentration provided by CS enables the effective removal of NH_(4)^(+)from EMR and the solidification of Mn^(2+)during thermal reactions.
文摘Zinc （Zn） is essential to plant growth and relatively mobile in soils. This study was conducted to assess the effect of common ions （Ca2＋, K＋, Na＋, NH＋, CI-, NO3-, and H2PO4） on sorption of Zn in surface samples of ten calcareous soils from western Iran using 10 mmol L-1 KC1, KNO3, KH2P04, Ca（N03）2, NAN03, and NH4N03 solutions as background electrolytes. The results indicated that both NH＋, K＋, and Ca2＋ equally decreased Zn sorption as compared to Na＋. Zinc sorption was decreased by H2PO4- as compared to NO3 and Cl-. The Langmuir and Freundlich equations fitted closely to the sorption data of all ions. The Langmuir maximum, bonding energy constant, and Freundlich distribution coefficient for Zn sorption differed among the various ionic background electrolytes. Langmuir sorption parameters showed that the presence of H2PO4- decreased the maximum Zn adsorbed, but increased the bonding energy. Although K＋ and NH＋ equally influenced maximum Zn adsorbed, they differed in their effect on the distribution coefficient of Zn in soils. Values of saturation index calculated using Visual MINTEQ indicated that at the low Zn concentration, Zn solubility was controlled by sorption reactions and at the high Zn concentration, it was mainly controlled by sorption and mineral precipitation reactions, such as precipitation of Zn3（PO4）2.4H2O, Zn5（OH）6（CO3）2, and ZnCO3. For most ionic background electrolytes, soil pH, CaC03, and cation exchange capacity （CEC） were significantly correlated with sorption parameters.
文摘A new thermodynamic model derived from a Helmholtz energy function is established by considering the contribution of various particle interactions in the electrolyte solutions to calculate the solubility of gases in aqueous electrolytes. A good agreement between the experimental data and calculation results is obtained. Meanwhile, the results show that this model is superior to the MPT EOS under elevated pressure.
