Solid-state synthesis and ion transport characteristics of the β-KSbF_(4) for all-solid-state fluoride-ion batteries

All-solid-state fluoride ion batteries(FIBs)have been recently considered as a post-lithium-ion battery system due to their high safety and high energy density.Just like all solid-state lithium batteries,the key to the development of FIBs lies in room-temperature electrolytes with high ionic conductivity.β-KSbF_(4) is a kind of promising solid-state electrolyte for FIBs owing to its rational ionic conductivity and relatively wide electrochemical stability window at room temperature.However,the previous synthesis routes ofβ-KSbF_(4) required the use of highly toxic hydrofluoric acid and the ionic conductivity of as-prepared product needs to be further improved.Herein,the β-KSbF_(4) sample with an ionic conductivity of 1.04×10^(-4)s cm^(-1)(30°C)is synthesized through the simple solid-state route.In order to account for the high ionic conductivity of the as-synthesizedβ-KSbF_(4),X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive X-ray spectroscopy(EDS)are used to characterize the physic-ochemical properties.The results show that the as-synthesizedβ-KSbF_(4) exhibits higher carrier concentra-tion of 1.0×10^(-6)S cm-Hz^(-1)K and hopping frequency of 1.31×10^(6)Hz at 30°C due to the formation of the fluorine vacancies.Meanwhile,the hopping frequency shows the same trend as the changes of ionic conductivity with the changes of temperature,while the carrier concentration is found to be almost con-stant.The two different trends indicate the hopping frequency is mainly responsible for the ionic conduc-tion behavior withinβ-KSbF_(4).Furthermore,the all-solid-state FIBs,in which Ag and Pb+PbF_(2) are adopted as cathode and anode,andβ-KSbF_(4) as fluoride ion conductor,are capable of reversible charge and discharge.The assembled FIBs show a discharge capacity of 108.4 mA h g^(-1) at 1st cycle and 74.2 mA h g^(-1) at 50th cycle.Based on an examination of the capacity decay mechanism,it has been found that deterioration of the electrolyte/electrode interface is an important reason for hindering the commer-cial application of FIBs.Hence,the in-depth comprehension of the ion transport characteristics inβ-KSbF_(4) and the interpretation of the capacity fading mechanism will be conducive to promoting development of high-performanceFIBs.

Effect of fluoride ions on coordination structure of titanium in molten NaCl–KCl

The effects of fluoride ions(F^(-)) on the electrochemical behavior and coordination properties of titanium ions(Ti^(n+)) were studied in this work,by combining electrochemical and mathematical analysis as well as spectral techniques.The α was taken as a factor to indicate the molar concentration ratio of F^(-) and Ti^(n+).Cyclic voltammetry(CV),square wave voltammetry(SWV),and open circuit potential method(OCP)were used to study the electrochemical behavior of titanium ions under conditions of various α,and in-situ sampler was used to prepare molten salt samples when α equal to 0.0,1.0,2.0,3.0,4.0,5.0,6.0,and 8.0.And then,samples were analyzed by X-ray photoelectron spectroscopy(XPS) and Raman spectroscopy.The results showed that F^(-) in molten salt can reduce the reduction steps of titanium ions and greatly affects the proportion of valence titanium ions which making the high-valence titanium content increased and more stable.Ti^(2+) cannot be detected in the molten salt when α is higher than 3.0 and finally transferred to titanium ions with higher valence state.Investigation revealed that the mechanism behind those phenomenon is the coordination compounds(TiCl_(j) F_(i)^(m-)) forming.

Fluoride Ion Adsorption Effect and Adsorption Mechanism of Self-Supported Adsorbent Materials Based on Desulfurization Gypsum-Aluminate Cement

The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-exchange adsorption properties of layered double hydroxides(LDHs).Self-supported porous adsorbent materials loaded with AFm and AFt were prepared from a composite cementitious system consisting of calcium aluminate cement(CAC)and flue gas desulfurization gypsum(FGDG)by chemical foaming technique.The mineral composition of the adsorbent material was characterized by X-ray diffraction(XRD)and Scanning electron microscopy(SEM).Through the static adsorption experiment,the adsorption effect of the mineral composition of the adsorbent on fluoride ions was deeply analyzed,and the adsorption mechanism was revealed.XRD and SEM showed that the main hydration phases of the composite cementitious system consisting of CAC and FGDG are AFm,AFt,AH_(3),and CaSO_(4)·2H_(2)O.FGDG accelerates the hydration process of CAC and inhibits the transformation of AFt to AFm.The AFt content increased,and the AFm content decreased or even disappeared as the amount of FGDG increased.Static adsorption experiment results showed that AFm and AFt in adsorbent materials could significantly enhance the adsorption of fluoride ions.The adsorption of F^(−)in aqueous solution by PAG tends more towards monolayer adsorption with a theoretical maximum capacity of 108.70 mg/g and is similar to the measured value of 112.77 mg/g.

Application of ion chromatography to the determination of water-soluble inorganic and organic ions in atmospheric aerosols

A simple, sensitive and convenient ion chromatography(IC) method was established for the simultaneous determination of twelve water-soluble inorganic anions(F -, Cl -, NO - 2, NO - 3, SO 2- 3, SO 2- 4, PO 3- 4), and fifteen water-soluble organic ions(formate, acetate, MSA, oxalate, malonate, succinate, phthalates, etc.) in atmospheric aerosols. The linear concentrations ranged from 0.005 μg/m 3 to 500 μg/m 3(r = 0.999—0.9999). The relative standard deviation(RSD) were 0.43%—2.00% and the detection limits were from 2.7 ng/m 3 to 88 ng/m 3. The proposed method was successfully applied to the simultaneous determination of those inorganic ions and organic ions in PM 2.5 of Beijing.

On-line Measurement of Water-Soluble Ions in Ambient Particles

Combining the system of rapid collection of ambient particles and ion chromatography, the system of rapid collection of fine particles and ion chromatography （RCFP-IC） was established to automatically analyze on-line the concentrations of water-soluble ions in ambient particles. Here, the general scheme of RCFP-IC is described and its basic performance is tested. The detection limit of RCFP-IC for SO4^2-, NO3^-, NO2^-, Cl^- and F- is below 0.3μg m^-3. The collection efficiency of RCFP-IC increases rapidly with increasing sized particles. For particles larger than 300 nm, the collection efficiency approaches 100%. The precision of RCFP-IC is more than 90% over 28 repetitions. The response of RCFP-IC is very sensitive and no obvious cross-pollution is found during measurement. A comparison of RCFP-IC with an integrated filter measurement indicates that the measurement of RCFP-IC is comparable in both laboratory experiments and field observations. The results of the field experiment prove that RCFP-IC is an effective on-line monitoring system and is helpful in source apportionment and pollution episode monitoring.

Preparation and Characterization of the Modified Polyvinylidene Fluoride (PVDF) Hollow Fibre Microfiltration Membrane

A novel thermally induced graft polymerization technique was used to modify a polyvinylidene fluoride （PVDF） hollow fibre microfiltration membrane. An artificial neural network （ANN） was applied to optimize the prepared condition of the membrane. The optimized dosing of acrylic acid （AA）, acrylamide （AM）, N, N＇- methylenebisacrylamide （NMBA） and potassium persulphate （KSP） designed by ANN was that AA was 40.63 ml/L; AM acted as 6.25 g/L; NMBA was 1.72 g/L and KSP was 1.5 g/L, respectively. The thermal stability of the PVDF modified hollow fibre membrane （PVDF-PAA） was investigated by thermogravimetric （TG） and differential scanning calorimetry （DSC） analysis. The polycrystallinity of the PVDF-PAA membrane was evaluated by X-ray diffraction （XRD） analysis. The complex formation of the modified membrane was ascertained by Fourier transform infrared spectroscopy （FTIR）. The morphology of the PVDF-PAA membrane was studied by environmental scanning electron microscopy （ESEM）. The surface compositions of the membrane were analyzed by X-ray photoelectron spectroscopy （XPS）. The adsorption capacity of Cu^2＋ ion on the PVDF-PAA hollow fibre membrane was also investigated.

Fluoride Removal by Lanthanum Alginate Bead: Adsorbent Characterization and Adsorption Mechanism

Lanthanum alginate bead is a new, highly active adsorbent. In the present study, we investigated its ad- sorption performance and its adsorption mechanism. The adsorption isotherm for fluoride onto lanthanum alginate b ead fits the Langmuir model well, and the maximum adsorption capacity is 197.2 mg·g-1. X-ray diffraction shows the amorphous nature of lanthanum alginate bead, which allows for better accessibility to fluoride and thus better activity. Infrared spectra of lanthanum alginate bead before and after adsorption confirm its stable skeletal structure. Scanning electron microscopy shows that the dense surface structure of the adsorbent appear cracks after adsorption. T he adsorption mechanism of lanthanum alginate bead is considered as an ion exchange between F- and Cl- or OH-, as verified from the adsorbent and the solution by pH effect, energy dispersive X-ray, and ion chromatography.

A fluorescent probe for fluoride ion based on 2-aminopyridyl-bridged calix[6]arene

An 2-anfinopyddyl-bddged calix[6]arene on the upper rim fixed in cone conformation （3） was successfully synthesized and its highly selective recognition towards fluoride ion was proved by fluorescent and 1H NMR titration experiments.

Fluorine in drinking water and urine in the urban and rural areas of northwestern China——Its determination by a fluoride ion selective electrode

In this study, the author determined fluorine in drinking water and urine of residents who are divided into four age groups (5, 12, 35-44, 65-74 aged), living in Huangling City, Shaanxi Province and at 6 villages of Qin'an County, Gansu Province, P.R.China. Some residents are living in fluorine exposure areas. A total of 929 residents (463 females and 466 males) involved in the study were selected from 7 tap water systems. Drinking water samples were collected from each area and analyzed using the fluoride ion-selective method. No positive correlation relationship was found between fluorine concentrations in urine and those in drinking water in the area where the fluorine concentrations of drinking water are within the range of 1-2 mg/L. The fluorine absorbed by resistents of different ages is different in amount. With the same concentrations of fluorine in drinking water, more fluorine would be absorbed by young residents than old residents. No difference can be seen in absorption amount of fluorine among different genders.

Diurnal variations of water-soluble ions in PM_(2.5)in Shanghai

Thirty-six daily time interval PM2.5 samples were collected in different seasonal dates in urban Shanghai, and the concentrations of four anions （Cl- , NO3-, SO4^2-, C2O4^2-） and five cations （NH＋, Na＋, K＋, Ca2＋, Mg2＋） were analyzed with ion chromatography. Sulfate, nitrate and ammonium were found to be the dominant species, accounting for about 80% of the total ions. The daily nitrate to sulfate mass ratio ranged from 0.31 to 0.82, indicating that coal combustion was still the main pollution source in Shanghai. The equivalent ratio of ammonium to stun of nitrate and sulfate showed fixed diurnal variation pattern in all the sampling days with higher values in the nighttime, suggesting that fine particles in the night were more neutralized. The oxalate to sulfate ratio was lower in the winter sampling days than that in hotter summer and autumn sampling days. Oxalate was significantly correlated with sulfate in winter sampling days, but not in the summer and autumn, suggesting that the formation mechanism of oxalate and sulfate was similar in winter, however different in hot days.

Concentrations,sources,and influential factors of water-soluble ions of atmospheric particles in Dunhuang Mogao Grottoes,a world heritage site in China

Atmospheric particle pollution is one of the major factors leading to degradation of ancient wall paintings,particularly heritage sites in arid and semi-arid regions.However,current systematic research on the changes,sources,and influential factors of atmospheric particulate matter and its water-soluble ion concentrations is not sufficient.Thus,the major water-soluble ion concentrations,sources,and influential factors of atmospheric particles PM_(2.5) and PM_(10)(particulate matter with an aerodynamic equivalent diameter≤2.5 and 10.0μm,respectively,in ambient air)were collected from Cave 16 and its ambient exterior environment in the Dunhuang Mogao Grottoes,China,between April 2015 and March 2016.Results showed that the concentrations of PM_(2.5) and PM_(10) inside and outside the cave were the highest in March 2016 and the lowest in December 2015.The higher particle concentration from March to May was related to the frequent occurrence of sand and dust events,and the lower particle concentration from June to September was associated with good diffusion conditions,increased precipitation,and an established cave shelterbelt.The concentration of particulate matter inside the cave was affected by the concentration of particles in the air outside the cave.Ca2+,NH+4,Na+,Cl-,and SO2-4were the main components of the total ions of PM_(2.5) and PM_(10) both inside and outside the cave.The total ions inside the cave were frequently affected by the disturbance of tourists'activities during the peak tourist season from May to August.Under the influence of dust,the total concentrations of Cl-,SO2-4,Na+,NH+4,and Ca2+in particles of different sizes inside and outside the cave increased,and the concentrations of Cl-,SO2-4,Na+,and Ca2+decreased during precipitation period.Backward air mass trajectory analysis suggested that the pollutants were mainly from Xinjiang,China.The pollutant sources of air particulates are straw burning,secondary pollution sources,soil dust,dry spring rivers,and tourist activities.

Determination of Boron Trifluoride in Boron Trifluoride Complex by Fluoride Ion Selective Electrode

A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride. The simulation indicated that the permissible aluminum masked at a certain p H value was limited and hardly related to F-concentration and boric acid. It is better to control p H value below 11.5 and the aluminum concentration within 0.025 mol/L to minimize the interference of hydroxide to the fluoride ISE. The decomposition conditions of boron trifluoride by aluminum chloride were investigated. It is found that the F-detection ratio will approach 1.0 if the Al/F molar ratio is 0.3—0.7 and aluminum concentration is no more than 0.02 mol/L when heated at 80 ℃ for 10 min. In one word, hydroxide is quite fit to mask aluminum for samples which contain high content of fluoride and aluminum and the BF3 content can be successfully determined by this method.

Up-Conversion Properties of Oxy-Fluoride Glasses Co-Doped with Ho^(3+) and Yb^(3+)

Oxy-fluoride glasses with composition of 25SiO2-65PbF2-9.4AlF3-0.1HoF3-0.5YbF3 were prepared. Their up-conversion fluorescence characteristics were investigated by 980 nm laser. Two emission peaks were observed at 540 and 650 nm. The up-conversion mechanism and processes were analyzed. The relationship between pumping power and relative intensity of emissions was discussed. From the dependence, it is known that the emissions centered at 540 and 650 nm are both attributed to two-photon process.

PREPARATION AND CHARACTERIZATION OF ION EXCHANGE MEMBRANES BASED ON POLYVINYLIDENE FLUORIDE

A new ion exchange membrane based on polyvinylidene fluoride (PVDF) and sulfonated poly(styrene-divinylbenzene) was prepared by in-situ polymerization. The incorporation of sulfonic groups into the polyvinylidene fluoride composite membrane was confirmed by infrared spectroscopy (IR), ion exchange capacity (IEC) and energy dispersive X-ray analysis (EDAX). Area resistance, IEC and water uptake of the treated membrane were evaluated. When 20% of the crosslinked membrane was sulfonated at 80degreesC for 22 h, the PVDF ion exchange membrane can attain 0.8 Omega . cm(2) area resistance in NaCl aqueous solution at 25degreesC, IEC is as high as 2.43 millimoles per grain of the wet membrane. The hydrophilicity of PVDF membrane is also significantly improved after treatment. When 60% of crosslinked membrane was sulfonated at 80degreesC for 6 h, water uptake of the treated membrane can attain 64.7%.

Preparation of CeO_2-TiO_2/SiO_2 and Its Removal Properties for Fluoride Ion

The CeO 2 TiO 2/SiO 2 surface composites were prepared by sol gel method using SiO 2 as substrate and CeO 2 TiO 2 as coating film. The removal capabilities of the composities for fluoride ion and the influences of environment conditions of the preparation on the coating quality and removal capacities of F - were studied by experiments. SEM was used to study the surface morphologies of the films obtained. It is proved that n Ti(OC 4H 9) 4 / n CeCl 3·7H 2O =1, n CH 3COOH / n Ti(OC 4H 9) 4 =4 5, n C 3H 8O 3 / n Ti(OC 4H 9) 4 =0 3, R H=95% and t 110 ℃ are the acceptable conditions to get the surface composite whose adsorbent capacity( q ) and removal ratio( E ) for F - are 21 4 mg/g and 85 6% respectively.

Real-Time Observation on Water-Soluble Ions of PM_(2.5)in Beijing under the Influences of Different Air Masses in Summer

To further understand the variations of water-soluble ions in PM2.5 in Beijing,the authors observed their concentrations continuously and in high temporal resolution by the system for rapid collection of fine particles and ion chromatography(RCFP-IC) during 12–18 July 2010.These results combined with those of earlier backward trajectory research are used analyzed to determine the causes of concentration changes in water-soluble ions under the influences of two kinds of air masses in summer.The results indicate that concentrations of NO3-,SO42-,and NH4+ were influenced strongly by the continental air mass than by the marine air mass.Cl- and Na+ were not changed significantly.Because the sources of K+,Mg2+,and Ca2+ are mainly concentrated on land,their concentration levels were slightly higher under the control of continental air mass than that of the marine air mass.Variations of NO2- during the observation differed from those of other ions;its concentration was significantly higher under the influence of marine air mass.Moreover,the authors obtain the diurnal variations of eight water-soluble inorganic ions including NH4+,K+,Mg2+,Ca2+,Cl-,NO2-,NO3-,and SO42-.Diurnal variations of NH4+,NO3-,and Cl- showed single peak,which appeared before noon,while SO42- showed two peaks that appeared during rush hours.Those of Mg2+,Ca2+,and K+ showed single peak that appeared in the afternoon.That of NO2- showed with a peak appearing at sunrise and a valley appearing at sunset.

Dynamic Corrosion Trail of Ti-6Al-4V Alloy in Acid Artificial Saliva Containing Fluoride Ion

The dynamic corrosion behaviors of Ti-6Al-4V alloy in acid artificial saliva containing fluoride ion were traced using electrochemical techniques,optical microscope,scanning electron microscopy,energy dispersive spectrometer and roughness tester.The experimental results indicate that a negative shift of corrosion potential as well as a continuous decrease in impedance for the alloy exists with increasing immersion time,and the degradation rate of the alloy presents the trend of first increase then decrease following the dissolution of passivation film and the formation of corrosion products.The accumulated fluoride ion on the alloy surface accelerates the fracture of passivation film,and the occurrence and development of corrosion of alloy are mainly located at the sites where the formation and shedding of white particles are composed of fluoride compounds,resulting in the decrease of corrosion resisting property of the alloy.A possible model is proposed to elaborate the dynamic corrosion behavior of the alloy.

Determination of Fluoride in Various Samples Using a Fluoride Selective Electrode

Fluoride is widespread in the environment, water, air, vegetation and Earth’s crust which can entre ground and surface water by natural process. Fluoride in minute quantities is essential component for human health and help in normal mineralization of bone and formation of dental enamel. The determination of fluoride in some species was performed by using fluoride ion-selective electrode by direct measurement and standard addition method. The concentration of fluoride ion was determined in drinking water (from different place at Kathmandu), toothpaste, various brand of tea and coffees. The range of fluoride concentration in water sample was 0.16 to 0.39 mg/l, tea and coffee samples were 0.011 to 0.084 mg/l and its value of toothpaste was 0.026 to 0.75 mg/l. The concentration of fluoride ion obtain from different sample was compared with the legitimate value given by the world health organization.

REPLACED SITE OF Eu^(2+) ION IN THE COMPLEX FLUORIDES WITH THE PEROVSKITE CRYSTAL STRUCTURE

The replaced site of Eu^(2+) ion is dependent on the electronegativity difference of the cations in complex fluorides.In the mixed fluoride KMgF_3:Eu^(2+),Eu^(2+) ion occupies K^+ site,its emission spectrum is a sharp line and its valence-state is stable.

Characterization of Fluoride Phosphors for Diode Pumped Solid-State Lighting Applications

Phosphor coated diodes are critical to the lighting industry. Rare-earth doped fluoride phosphors are characterized in this work. Spectroscopy and lifetime measurements of CaF2: Dy3+, LaF3: Eu3+ and Tb3+-doped LaF3 and CaF2 crystals were performed by irradiating the samples with 405 and 375 nm diode lasers. Chromaticity diagrams are developed from spectral measurements. Dy3+-doped CaF2 revealed bright white light emission having peaks at 492, 570 and 654 nm. The measured color coordinates are x = 0.322 and y = 0.340 for Dy3+-doped CaF2 and these values are close to those of sunlight and the coordinated color temperature is 6147 K, under 405 m laser excitation. Eu3+-doped LaF3 revealed twenty emission peaks in the visible wavelength region. The color coordinates measured for LaF3: Eu3+ are x = 0.283 and y = 0.293 under 405 nm diode laser excitation and the color temperature is 9557 K. Eu3+-doped LaF3 provides cool white-light, under 405 nm diode laser excitation. Tb3+-doped fluoride crystals revealed bright white light under low power diode laser excitation. The measured color coordinates for Tb3+-doped CaF2 are x = 0.329 and y = 0.558 and the color temperature is 7713 K. The color coordinates for LaF3: Tb3+ are x = 0.342 and y = 0.365 and the coordinated color temperature is 5370 K. These values are close to those of sunlight.