The anoxic decomposition and influence of carbon precursors on the properties of LiFePO_4/C prepared by using Fe_2O_3 were investigated.X-ray powder diffractometry,Fourier transform infrared spectroscopy(FTIR),scannin...The anoxic decomposition and influence of carbon precursors on the properties of LiFePO_4/C prepared by using Fe_2O_3 were investigated.X-ray powder diffractometry,Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM) and carbon content and charge–discharge tests were applied to the characterization of the as-synthesized cathodes.Partial carbon is lost in the anaerobic decomposition of organic precursors and a high hydrogen content leads to a high residual carbon rate.Pyromellitic anhydride and citric acid participate in reactions before and in ball-milling.All the chosen carbon precursors are capable of producing LiFePO_4 with high degree of crystallinity and purity.The carbon derived from α-D-glucose,pyromellitic anhydride,soluble starch,citric acid and polyacrylamide has a loose and porous texture in LiFePO_4/C which forms conduction on and between LiFePO_4 particles.LiFePO_4/C prepared by using α-D-glucose,pyromellitic anhydride,citric acid and sucrose exhibits appreciable electrochemical performance.Graphite alone is able to enhance the electrochemical performance of LiFePO_4 to a limited extent but incapable of preparing practical cathode.展开更多
The impregnation of a special grade PAN precursor,fibers wus carried out in a 8 wt% KMnO4 aqueous solution to obtain modified PAN precursor fibers. The effects of modification on the chemical stncture and the mechani...The impregnation of a special grade PAN precursor,fibers wus carried out in a 8 wt% KMnO4 aqueous solution to obtain modified PAN precursor fibers. The effects of modification on the chemical stncture and the mechanical properties of precursor fibers thermally stabilized and their resulting carbon fibers u'ere characterized by the combiination use of densities, wide-angle X-ray diffraction (WAXD), X-ray photoelectron speetroscopy (XPS), elemental analysis ( EA ), Fourier traasform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM), etc.KMnO4 as a strong oxidizer can swell, oxidize and corrode the skin of a precursor.fiber, and transform C≡N groups to C≡N ones, meamchile , it can decreuse the crystal .size increuse the orientation index and the costallinity index, furthermore it can increuse the densities of modified PAN precursors and resuhing thermally stabilized fibers. As a result, the carbon fibers developed from modified PAN fibers show an improvement in tensile strength of 31.25 % and an improvement in elongation of 77.78 % , but a decrease of 16. 52% in Young's modulus.展开更多
Structural changes in carbon fibers at each stage of, especially, preoxidation process are well known to play a great role in achieving the ultimate product quality. Differential scanning calorimetry (DSC), scanning e...Structural changes in carbon fibers at each stage of, especially, preoxidation process are well known to play a great role in achieving the ultimate product quality. Differential scanning calorimetry (DSC), scanning electron microscope (SEM), density method and optical microscope were used to characterize the preoxidation extent. A conventional approach, e.g., density aim, to evaluate the extent of preoxidation is not very exact. A DSC curve of a PAN precursor only can provide general information, major in the temperature regime of preoxidation reaction. However, the evaluation of a preoxidation extent, especially from conventional preoxidation temperature with a great span regime of 200~400癈, is put forward in this paper, in which the evolution of core/shell morphological structure is a kind of straightforward evidence.展开更多
Thermal mechanical analysis,FT-IR,WAXD and some conventional measurements,such as densities and mechanical properties,were used to characterize the effect of the modification using KMnO4 and SnCl4 on the thermal mecha...Thermal mechanical analysis,FT-IR,WAXD and some conventional measurements,such as densities and mechanical properties,were used to characterize the effect of the modification using KMnO4 and SnCl4 on the thermal mechanical behaviors and structural changes during the process of thermal stabilization of modified PAN precursors.Compared to the unmodified original PAN precursors,some conclusions were drawn that the thermal stabilization starts at a lower temperature for modified PAN fibers,for example,the peak of thermal stress changes for modified PAN precursors using KMnO4 displays a decrease of 20℃ and a increase of 30% in the ultimate thermal stress,that chemical modification makes structural transformation perfect and increases by 25% of the thermal stress at the temperature range of 230℃-300℃,that the modified PAN fibers display an increase of 100% in the thermal strain,once after pre-oxidized,show an increase of 7.8% in orientation index,and a decrease of 9.9% in crystal size for identical preload in the region of 13.1-14.5MPa.It was also concluded that the modification using SnCl4 would alleviate the changes in physical and chemical stress regimes and result in improvement in structure and decrease in defects.展开更多
The precursor carbonization method was first applied to prepare W–C compound powder to perform the in-situ synthesis of the WC phase in a Fe-based alloy coating. The in-situ formation mechanism during the cladding pr...The precursor carbonization method was first applied to prepare W–C compound powder to perform the in-situ synthesis of the WC phase in a Fe-based alloy coating. The in-situ formation mechanism during the cladding process is discussed in detail. The results reveal that fine and obtuse WC particles were successfully generated and distributed in Fe-based alloy coating via Fe/W–C compound powders. The WC particles were either surrounded by or were semi-enclosed in blocky M7C3 carbides. Moreover, net-like structures were confirmed as mixtures of M23C6 and α-Fe; these structures were transformed from M7C3. The coarse herringbone M6C carbides did not only derive from the decomposition of M7C3 but also partly originated from the chemical reaction at the α-Fe/M23C6 interface. During the cladding process, the phase evolution of the precipitated carbides was WC → M7C3 → M23C6 + M6C.展开更多
When adding sufficient chlorine to achieve breakpoint chlorination to source water containing high concentration of ammonia during drinking water treatment, high concentrations of disinfection by-products(DBPs) may ...When adding sufficient chlorine to achieve breakpoint chlorination to source water containing high concentration of ammonia during drinking water treatment, high concentrations of disinfection by-products(DBPs) may form. If N-nitrosamine precursors are present, highly toxic N-nitrosamines, primarily N-nitrosodimethylamine(NDMA), may also form. Removing their precursors before disinfection should be a more effective way to minimize these DBPs formation. In this study, zeolites and activated carbon were examined for ammonia and N-nitrosamine precursor removal when incorporated into drinking water treatment processes.The test results indicate that Mordenite zeolite can remove ammonia and five of seven N-nitrosamine precursors efficiently by single step adsorption test. The practical applicability was evaluated by simulation of typical drinking water treatment processes using six-gang stirring system. The Mordenite zeolite was applied at the steps of lime softening, alum coagulation, and alum coagulation with powdered activated carbon(PAC) sorption. While the lime softening process resulted in poor zeolite performance, alum coagulation did not impact ammonia and N-nitrosamine precursor removal. During alum coagulation, more than67% ammonia and 70%–100% N-nitrosamine precursors were removed by Mordenite zeolite(except 3-(dimethylaminomethyl)indole(DMAI) and 4-dimethylaminoantipyrine(DMAP)). PAC effectively removed DMAI and DMAP when added during alum coagulation. A combination of the zeolite and PAC selected efficiently removed ammonia and all tested seven N-nitrosamine precursors(dimethylamine(DMA), ethylmethylamine(EMA), diethylamine(DEA), dipropylamine(DPA), trimethylamine(TMA), DMAP, and DMAI) during the alum coagulation process.展开更多
The nanopore structures in precursors Four carbon-fiber precursors are prepared. They are crucial to the performance of PAN-based carbon fibers are bath-fed filaments (A), water-washing filaments (B) hot-stretchin...The nanopore structures in precursors Four carbon-fiber precursors are prepared. They are crucial to the performance of PAN-based carbon fibers are bath-fed filaments (A), water-washing filaments (B) hot-stretching filaments (C) and drying-densification filaments (D). Synchrotron radiation small angle X-ray scattering is used to probe and compare the nanopore structures of the four fibers. The nanopore size, discrete volume distribution, nanopore orientation degree along the fiber axis and the porosity are obtained. The results demonstrate that the nanopores are mainly formed in the water-washing stage. During the processes of the subsequent production technologies, the slenderness ratio of nanopores and their orientation degree along the fiber axis increase further and simultaneously, the porosity decreases. These results are helpful for improving the performance of the final carbon fibers.展开更多
In this paper,two carbon-coated lithium titanate(LTO-C1 and LTO-C2)composites were synthesized using the ball-milling-assisted calcination method with different carbon precursor addition processes.The physical and ele...In this paper,two carbon-coated lithium titanate(LTO-C1 and LTO-C2)composites were synthesized using the ball-milling-assisted calcination method with different carbon precursor addition processes.The physical and electrochemical properties of the as-synthesized negative electrode materials were characterized to investigate the effects of two carbon-coated LTO synthesis processes on the electrochemical performance of LTO.The results show that the LTO-C2 synthesized by using Li2CO3 and TiO2 as the raw materials and sucrose as the carbon source in a one-pot method has less polarization during lithium insertion and extraction,minimal charge transfer impedance value and the best electrochemical performance among all samples.At the current density of 300 mA·h·g^(-1),the LTO-C2 composite delivers a charge capacity of 126.9 mA·h·g^(-1),and the reversible capacity after 300 cycles exceeds 121.3 mA·h·g^(-1) in the voltage range of 1.0–3.0 V.Furthermore,the electrochemical impedance spectra show that LTO-C2 has higher electronic conductivity and lithium diffusion coefficient,which indicates the advantages in electrode kinetics over LTO and LTO-C1.The results clarify the best electrochemical properties of the carbon-coated LTO-C2 composite prepared by the one-pot method.展开更多
Cerium dioxide was used for the first time as reactive sorbent for the degradation of the organophosphate pesticides para-thion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some ch...Cerium dioxide was used for the first time as reactive sorbent for the degradation of the organophosphate pesticides para-thion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some chemical warfare agents-nerve gases soman and O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate (VX). CeO2 specimens were prepared by calcination of basic cerous carbonate obtained by precipitation from an aqueous solution. The CeO2 samples containing certain amounts (1 wt.%-5 wt.%) of the neighboring lanthanides (La, Pr, Nd) were prepared in a similar way from pure lanthanide salts. It was shown that ceria accelerated markedly the decomposition of parathion methyl causing the cleavage of the P-O-aryl bond in the pesticide molecule. A similar reaction mechanism was proposed for the degradation of other organophosphate pesticides and nerve agents. The degradation times (reaction half-times) were in an order of minutes in the presence of CeO2, compared to hours or days under common environ-mental conditions. The reaction in suitable organic solvents allowed conversions of about 90%for parathion methyl loading of 20 mg pesticide/g CeO2 within 2 h with a reactant half-life in the order of 0.1 min. The key parameter governing the degradation efficiency of CeO2 was the temperature during calcination. At optimum calcination temperature (about 773.15 K), the produced ceria retained a sufficiently high surface area, and attained an optimum degree of crystallinity (related to a number of crystal defects, and thus poten-tial reactive sites). The presence of other lanthanides somewhat decreased the reaction rate, but this effect was not detrimental and permitted the possible use of chemically impure ceria as a reactive sorbent. A fast organophosphate degradation was demonstrated not only in non-polar solvents (such as heptane), but also in polar aprotic solvents (acetonitrile, acetone) that are miscible with water. This opens new possibilities for designing more versatile decontamination strategies. The cleavage of phosphate ester bonds is of a great importance not only for the degradation of dangerous chemicals (chemical weapons, pesticides), but also for interactions of ceria (es-pecially the nano-sized one) in biologically relevant systems.展开更多
基金Project(2010ZC051)supported by Natural Science Foundation of Yunnan Province,ChinaProject(20140439)supported by Analysis and Testing Foundation of Kuming University of Science and Technology,ChinaProject(14118245)supported by the Starting Research Fund from Kunming University of Science and Technology,China
文摘The anoxic decomposition and influence of carbon precursors on the properties of LiFePO_4/C prepared by using Fe_2O_3 were investigated.X-ray powder diffractometry,Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM) and carbon content and charge–discharge tests were applied to the characterization of the as-synthesized cathodes.Partial carbon is lost in the anaerobic decomposition of organic precursors and a high hydrogen content leads to a high residual carbon rate.Pyromellitic anhydride and citric acid participate in reactions before and in ball-milling.All the chosen carbon precursors are capable of producing LiFePO_4 with high degree of crystallinity and purity.The carbon derived from α-D-glucose,pyromellitic anhydride,soluble starch,citric acid and polyacrylamide has a loose and porous texture in LiFePO_4/C which forms conduction on and between LiFePO_4 particles.LiFePO_4/C prepared by using α-D-glucose,pyromellitic anhydride,citric acid and sucrose exhibits appreciable electrochemical performance.Graphite alone is able to enhance the electrochemical performance of LiFePO_4 to a limited extent but incapable of preparing practical cathode.
基金Founded by the National Natural Science Foundation of China(No.50333070)
文摘The impregnation of a special grade PAN precursor,fibers wus carried out in a 8 wt% KMnO4 aqueous solution to obtain modified PAN precursor fibers. The effects of modification on the chemical stncture and the mechanical properties of precursor fibers thermally stabilized and their resulting carbon fibers u'ere characterized by the combiination use of densities, wide-angle X-ray diffraction (WAXD), X-ray photoelectron speetroscopy (XPS), elemental analysis ( EA ), Fourier traasform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM), etc.KMnO4 as a strong oxidizer can swell, oxidize and corrode the skin of a precursor.fiber, and transform C≡N groups to C≡N ones, meamchile , it can decreuse the crystal .size increuse the orientation index and the costallinity index, furthermore it can increuse the densities of modified PAN precursors and resuhing thermally stabilized fibers. As a result, the carbon fibers developed from modified PAN fibers show an improvement in tensile strength of 31.25 % and an improvement in elongation of 77.78 % , but a decrease of 16. 52% in Young's modulus.
基金the National Natural Science Foundatlon of China under grant No.50172004,50273002 ,50333070.
文摘Structural changes in carbon fibers at each stage of, especially, preoxidation process are well known to play a great role in achieving the ultimate product quality. Differential scanning calorimetry (DSC), scanning electron microscope (SEM), density method and optical microscope were used to characterize the preoxidation extent. A conventional approach, e.g., density aim, to evaluate the extent of preoxidation is not very exact. A DSC curve of a PAN precursor only can provide general information, major in the temperature regime of preoxidation reaction. However, the evaluation of a preoxidation extent, especially from conventional preoxidation temperature with a great span regime of 200~400癈, is put forward in this paper, in which the evolution of core/shell morphological structure is a kind of straightforward evidence.
基金HAIPURT (No2006KYCX009)National Natural Science Foundation of Henan,China (No200510465008)Henan Innovation Project of China(No0523021300)
文摘Thermal mechanical analysis,FT-IR,WAXD and some conventional measurements,such as densities and mechanical properties,were used to characterize the effect of the modification using KMnO4 and SnCl4 on the thermal mechanical behaviors and structural changes during the process of thermal stabilization of modified PAN precursors.Compared to the unmodified original PAN precursors,some conclusions were drawn that the thermal stabilization starts at a lower temperature for modified PAN fibers,for example,the peak of thermal stress changes for modified PAN precursors using KMnO4 displays a decrease of 20℃ and a increase of 30% in the ultimate thermal stress,that chemical modification makes structural transformation perfect and increases by 25% of the thermal stress at the temperature range of 230℃-300℃,that the modified PAN fibers display an increase of 100% in the thermal strain,once after pre-oxidized,show an increase of 7.8% in orientation index,and a decrease of 9.9% in crystal size for identical preload in the region of 13.1-14.5MPa.It was also concluded that the modification using SnCl4 would alleviate the changes in physical and chemical stress regimes and result in improvement in structure and decrease in defects.
基金financially supported by the National Natural Science Foundation of China (No. 51379070)
文摘The precursor carbonization method was first applied to prepare W–C compound powder to perform the in-situ synthesis of the WC phase in a Fe-based alloy coating. The in-situ formation mechanism during the cladding process is discussed in detail. The results reveal that fine and obtuse WC particles were successfully generated and distributed in Fe-based alloy coating via Fe/W–C compound powders. The WC particles were either surrounded by or were semi-enclosed in blocky M7C3 carbides. Moreover, net-like structures were confirmed as mixtures of M23C6 and α-Fe; these structures were transformed from M7C3. The coarse herringbone M6C carbides did not only derive from the decomposition of M7C3 but also partly originated from the chemical reaction at the α-Fe/M23C6 interface. During the cladding process, the phase evolution of the precipitated carbides was WC → M7C3 → M23C6 + M6C.
基金supported by US EPA STAR program(No.83517301)Missouri Department of Natural Resourcesthe support from Chemistry Department,Environmental Research Center,and Center for Single Nanoparticle,Single Cell,and Single Molecule Monitoring(CS3M)at Missouri University of Science and Technology
文摘When adding sufficient chlorine to achieve breakpoint chlorination to source water containing high concentration of ammonia during drinking water treatment, high concentrations of disinfection by-products(DBPs) may form. If N-nitrosamine precursors are present, highly toxic N-nitrosamines, primarily N-nitrosodimethylamine(NDMA), may also form. Removing their precursors before disinfection should be a more effective way to minimize these DBPs formation. In this study, zeolites and activated carbon were examined for ammonia and N-nitrosamine precursor removal when incorporated into drinking water treatment processes.The test results indicate that Mordenite zeolite can remove ammonia and five of seven N-nitrosamine precursors efficiently by single step adsorption test. The practical applicability was evaluated by simulation of typical drinking water treatment processes using six-gang stirring system. The Mordenite zeolite was applied at the steps of lime softening, alum coagulation, and alum coagulation with powdered activated carbon(PAC) sorption. While the lime softening process resulted in poor zeolite performance, alum coagulation did not impact ammonia and N-nitrosamine precursor removal. During alum coagulation, more than67% ammonia and 70%–100% N-nitrosamine precursors were removed by Mordenite zeolite(except 3-(dimethylaminomethyl)indole(DMAI) and 4-dimethylaminoantipyrine(DMAP)). PAC effectively removed DMAI and DMAP when added during alum coagulation. A combination of the zeolite and PAC selected efficiently removed ammonia and all tested seven N-nitrosamine precursors(dimethylamine(DMA), ethylmethylamine(EMA), diethylamine(DEA), dipropylamine(DPA), trimethylamine(TMA), DMAP, and DMAI) during the alum coagulation process.
基金Supported by National Natural Science Foundation of China (10835008)Knowledge Innovation Program of Chinese Academy of Sciences (KJCX3-SYW-N8)Momentous Equipment Program of Chinese Academy of Sciences (YZ200829)
文摘The nanopore structures in precursors Four carbon-fiber precursors are prepared. They are crucial to the performance of PAN-based carbon fibers are bath-fed filaments (A), water-washing filaments (B) hot-stretching filaments (C) and drying-densification filaments (D). Synchrotron radiation small angle X-ray scattering is used to probe and compare the nanopore structures of the four fibers. The nanopore size, discrete volume distribution, nanopore orientation degree along the fiber axis and the porosity are obtained. The results demonstrate that the nanopores are mainly formed in the water-washing stage. During the processes of the subsequent production technologies, the slenderness ratio of nanopores and their orientation degree along the fiber axis increase further and simultaneously, the porosity decreases. These results are helpful for improving the performance of the final carbon fibers.
文摘In this paper,two carbon-coated lithium titanate(LTO-C1 and LTO-C2)composites were synthesized using the ball-milling-assisted calcination method with different carbon precursor addition processes.The physical and electrochemical properties of the as-synthesized negative electrode materials were characterized to investigate the effects of two carbon-coated LTO synthesis processes on the electrochemical performance of LTO.The results show that the LTO-C2 synthesized by using Li2CO3 and TiO2 as the raw materials and sucrose as the carbon source in a one-pot method has less polarization during lithium insertion and extraction,minimal charge transfer impedance value and the best electrochemical performance among all samples.At the current density of 300 mA·h·g^(-1),the LTO-C2 composite delivers a charge capacity of 126.9 mA·h·g^(-1),and the reversible capacity after 300 cycles exceeds 121.3 mA·h·g^(-1) in the voltage range of 1.0–3.0 V.Furthermore,the electrochemical impedance spectra show that LTO-C2 has higher electronic conductivity and lithium diffusion coefficient,which indicates the advantages in electrode kinetics over LTO and LTO-C1.The results clarify the best electrochemical properties of the carbon-coated LTO-C2 composite prepared by the one-pot method.
基金Project supported by Czech Science Foundation(P106/12/1116)
文摘Cerium dioxide was used for the first time as reactive sorbent for the degradation of the organophosphate pesticides para-thion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some chemical warfare agents-nerve gases soman and O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate (VX). CeO2 specimens were prepared by calcination of basic cerous carbonate obtained by precipitation from an aqueous solution. The CeO2 samples containing certain amounts (1 wt.%-5 wt.%) of the neighboring lanthanides (La, Pr, Nd) were prepared in a similar way from pure lanthanide salts. It was shown that ceria accelerated markedly the decomposition of parathion methyl causing the cleavage of the P-O-aryl bond in the pesticide molecule. A similar reaction mechanism was proposed for the degradation of other organophosphate pesticides and nerve agents. The degradation times (reaction half-times) were in an order of minutes in the presence of CeO2, compared to hours or days under common environ-mental conditions. The reaction in suitable organic solvents allowed conversions of about 90%for parathion methyl loading of 20 mg pesticide/g CeO2 within 2 h with a reactant half-life in the order of 0.1 min. The key parameter governing the degradation efficiency of CeO2 was the temperature during calcination. At optimum calcination temperature (about 773.15 K), the produced ceria retained a sufficiently high surface area, and attained an optimum degree of crystallinity (related to a number of crystal defects, and thus poten-tial reactive sites). The presence of other lanthanides somewhat decreased the reaction rate, but this effect was not detrimental and permitted the possible use of chemically impure ceria as a reactive sorbent. A fast organophosphate degradation was demonstrated not only in non-polar solvents (such as heptane), but also in polar aprotic solvents (acetonitrile, acetone) that are miscible with water. This opens new possibilities for designing more versatile decontamination strategies. The cleavage of phosphate ester bonds is of a great importance not only for the degradation of dangerous chemicals (chemical weapons, pesticides), but also for interactions of ceria (es-pecially the nano-sized one) in biologically relevant systems.