Tuning the crystallinity of titanium nitride on copper-embedded carbon nanofiber interlayers for accelerated electrochemical kinetics in lithium-sulfur batteries

The development of lithium-sulfur(Li-S)batteries is hindered by the disadvantages of shuttling of polysulfides and the sluggish redox kinetics of the conversion of sulfur species during discharge and charge.Herein,the crystallinities of a titanium nitride(TiN)film on copper-embedded carbon nanofibers(Cu-CNFs)are regulated and the nanofibers are used as interlayers to resolve the aforementioned crucial issues.A low-crystalline TiN-coated Cu-CNF(L-TiN-Cu-CNF)interlayer is compared with its highly crystalline counterpart(H-TiN-Cu-CNFs).It is demonstrated that the L-TiN coating not only strengthens the chemical adsorption toward polysulfides but also greatly accelerates the electrochemical conversion of polysulfides.Due to robust carbon frameworks and enhanced kinetics,impressive highrate performance at 2 C(913 mAh g^(-1)based on sulfur)as well as remarkable cyclic stability up to 300 cycles(626 mAh g^(-1))with capacity retention of 46.5%is realized for L-TiN-Cu-CNF interlayer-configured Li-S batteries.Even under high loading(3.8 mg cm^(-2))of sulfur and relatively lean electrolyte(10μL electrolyte per milligram sulfur)conditions,the Li-S battery equipped with L-TiN-Cu-CNF interlayers delivers a high capacity of 1144 mAh g^(-1)with cathodic capacity of 4.25 mAh cm^(-2)at 0.1 C,providing a potential pathway toward the design of multifunctional interlayers for highly efficient Li-S batteries.

Crystallinity-defect matching relationship of g-C_(3)N_(4): Experimental and theoretical perspectives

Good crystallinity can reduce the charge recombination centers caused by defects,whilst structures with strong polycondensation have high charge mobility,leading to more charge transfer to the material surface for reaction.Much effort has been put into the preparation of a highly efficient g-C_(3)N_(4) with defects to improve its application potential under the premise in high crystallinity.Hence,this review paper emphasizes the importance to balance the defect and crystallinity of g-C_(3)N_(4).In addition,detailed discussion on the relationship between defects and activity of g-C_(3)N_(4) was carried out based on its applications in environmental purification(e.g.,VOCs oxidation,NO_(x) oxidation,H_(2)O_(2) evolution,sterilization,pesticide oxidation)and energy conversion(H_(2) evolution,N_(2) fixation and CO_(2) reduction).Lastly,the challenge in developing more efficient defective g-C_(3)N_(4) photocatalytic materials is summarized.

Influence of synthesis parameters on the crystallinity and Si/Al ratio of NaY zeolite synthesized from kaolin

Well-crystallized high-silica NaY zeolites （Si/Al〉2.5） were prepared from a reaction mixture consisting of metakaolin, sodium silicate solution and seed solution via optimization of the mixture composition and reaction conditions. The transformation from kaolin to high-silica NaY zeolite was confirmed by XRD, SEM and IR techniques. Subsequently, the influence of synthesis parameters, i.e. initial SIO2/Al2O3, initial Na2O/SiO2, initial H2O/SiO2, aging time of the seed solution, crystallization temperature and crystallization time, on the NaY growth was investigated in terms of crystallinity and Si/Al ratio. The results showed that the effects of initial SiO2/Al2O3, initial Na2O/SiO2 and initial H2O/ SiO2 on the crystaIlinity and Si/Al ratio of NaY zeolite are similar to those observed in the conventional syntheses of NaY zeolites only using sodium silicate solution as silicon source. However, due to the use of metakaolin as the main silicon and aluminum sources in the present study, a long crystallization induction period of 20 h was achieved, which can be attributed to the dissolution of metakaolin. In addition, different from the conventional syntheses of zeolite NaY, pure NaY zeolites （i.e. without NaP zeolite impurity） were still obtained even at 120℃ because of the use of a large quantity of seed solution （23 wt%） in the reaction mixture. As the aging time of the seed solution increased from 3.5 h to 22 h, the relative crystallinity of the NaY zeolite first increased sharply and then reached a plateau, while the Si/Al ratio first increased rapidly up to a maximum value of 2.75 corresponding to an aging time of 6.5 h, and then decreased sharply with the aging time.

Effects of crystallinity, {001}/{101} ratio, and Au decoration on the photocatalytic activity of anatase TiO_2 crystals

Anatase TiO2 nanocrystals and sub-microcrystals with truncated octahedral bipyramidal morphologies were prepared by direct calcination of TiOF2 precursors. The as-prepared TiO2 samples were thoroughly characterized by X-ray diffraction, Raman spectroscopy, field-emission scanning electron microscopy, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and UV-visible diffuse spectroscopy. It was found that the crystallinity, grain size, and {001}/{101} ratio of the samples can be increased by raising the calcination temperature from 500 to 800℃. The higher crystallinity and {001}/{101} facet ratio resulted in an increase in both aqueous and gas-phase photocatalytic activities, by inhibiting the recombination and separation of electrons and holes. After selecting two TiO2 samples with high crystallinity and {001}/{101} ratio, Au nanoparticles were decorated on their surfaces, and the photocatalytic activity of the resulting samples under visible light illumination was studied. It was found that the visible light-induced photocatalytic activity increased by 2.6 and 4.8 times, respectively, upon Au decoration of the samples prepared by calcination of TiOF2 at 700 and 800℃.

Illite Crystallinity Mapping of Very Low Grade Metamorphism of Triassic Metapelites in the Zoigê Area,Western China

X-ray diffraction methods for estimating the metamorphic grade of diagenetic, anchizone and epizone in metapelites are reviewed and applied to samples from a 7000 m＋ borehole in western China and surface samples from the surrounding Zoige area. Kiibler＇s illite crystallinity （IC） measurements provide more consistent results than calculated values of percentage of illite in the I/S mixed layers and percentage of I/S mixed layers. Down-borehole IC values display a typical burial metamorphic relationship between stratigraphic level and IC. A method for preparing very low grade metamorphic maps is described, and isograds plotted on a regional geological map at selected values of IC, delineating a high temperature diagenetic zone, an anchizone, and an epizone. The map shows that IC values are controlled by stratigraphic level in the north of the study area （i.e. burial metamorphism）, and proximity to an igneous intrusive body in the south （i.e. contact metamorphism）.

Influence of Synthesis Parameters with Low Seed Addition on the Crystallinity of ZSM-5

ZSM-5 zeolite microparticles （MPs） were synthesized under hydrothermal condition using a low crystal seed addition approach without template. The synthesis parameters such as the seed addition amount, the SiOJA1203 ratio, the aluminum source, the feeding addition method, aging, and crystallization were investigated. The structure, morphology and composition of the as-synthesized ZSM-5 zeolite MPs were characterized by X-ray powder diffraction （XRD）, scanning electron microscopy （SEM）, laser particle size distribution （PSD） measurements, and inductively coupled plasma-atomic emission spectrometry （ICP-AES）. The SIO2/A1203 ratio of ZSM-5 zeolite MPs was in the range of 20~80. The low seed addition was beneficial to improving the crystallinity and shortening the crystallization time, and the suitable amount of seed was 0.25% （SIO2）. The ZSM-5 zeolite MPs synthesized with aluminium nitrate nonahydrate used as the aluminum source exhibited a relatively high crystallinity. An appropriate aging time could eliminate the effect of feeding addition method and effectively adjust particle size. The particle size of ZSM-5 zeolite obtained at an aging time of 20 h was around 2.0 I.tm. Prolonging the aging time appropriately could also shorten the high-temperature crystallization time. The suitable aging time was 24 h, and the relative crystallinity of ZSM-5 zeolite could reach up to 99% after crystallization for 24 h at 180 ℃

Correlation between aggregation structure and tailing mineral crystallinity

Direct reduction is an emerging technology for the utilization of refractory iron ore. With this technology, iron oxides in the ore can be reduced to recoverable elemental iron. The structure of granular aggregates in direct reduction products was investigated by X-ray diffraction （XRD）. The results show that iron is mainly generated as a shell in the outer edge of the aggregates. The thermal conductivity of the iron shell is higher than that of other minerals. Thus, minerals close to the iron shell cool faster than those in the inner shells and do not crystallize well. These minerals mainly become stage 2 tailings. Hence the XRD intensity of stage 2 tailings is lower than that of stage 1 tailhags. When iron is mainly generated in the interior of the aggregates, the crystallinity of stage 2 tailings will be higher than that of stage 1 tailings. This indicates that the crystallinity of tailings can be used as a marker for the aggregate structure.

TEXTURE AND CRYSTALLINITY EVOLUTION IN ISOTACTIC POLYPROPYLENE INDUCED BY ROLLING AND THEIR INFLUENCE ON MECHANICAL PROPERTIES

The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isotactic polypropylene sheets were also measured in this work. The texture component method was used to analyze the rolling texture. The rolling texture consists mainly of （010）[001], （130）[001] and [001]//RD fiber components in the sample with a rolling true strain of 1.5. The results reveal that crystallinity drastically decreases during rolling. It is suggested that amorphization is a deformation mechanism which takes place as an alternative to crystallographic intralamellar slip depending on the orientation of the lamellae. Both the orientation and crystallinity affect the tensile mechanical properties of rolled polypropylene. Crystallinity influences the elastic modulus on both directions and yield strength on transverse direction at the first stage of deformation. Orientation is the main reason for the changes of mechanical properties, especially at the latter part of deformation. The changes of both tensile strength and elongation percentage on rolling direction are larger than those on transverse direction, which results from the orientation. At last, the anisotropic mechanical properties occur on the rolling and transverse direction： high tensile strength with low elongation percentage on rolling direction and low tensile strength with high elongation percentage on transverse direction.

Effect of Irradiation on Crystallinity and Mechanical Properties of Ultrahigh-Molecular-Weight Polyethylene

Ultrahigh-molecular-weight polyethylene(UtlMWPE) has been irradiated (0-40 Mrad) with a Co^(60) source at room temperature under vacuum. Their crystallinity has been investigated by DSC and SAXS A significant increase of heat of fusion can be seen at low irradiation doses, which is attributed to crystallization caused by chain scission during the process of irradiation. It is also observed that thickness of lamellae changes with irradiation dose. Young's modulus has been improved significantly after irradiation at low doses.

Different crystallinity of poly(d,l-lactide-co-p-dioxanone) copolymers acquired by control of chain microstructure

Poly（d,l-lactide-co-p-dioxanone） （P（LA-co-PDO）） copolymers with different chain microstructures were synthesized by onestep or two-step bulk ring-opening polymerizations of d,l-lactide （LA） and p-dioxanone （PDO） monomers using stannous octoate [Sn（Oct）2]/n-dodecanol as the initiating system. The average sequence lengths of the lactidyl （LLA） and dioxanyl （LpDo） units were calculated from the ^1H NMR spectra. It was found that both LLA and Lpoo values from the two-step syntheses were significantly longer than those from the corresponding one-step syntheses, indicating more blocky structure achieved for the twostep copolymers. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline, while the one-step copolymers were completely amorphous. In conclusion, the crystallinity of P（LA-co-PDO） copolymers could be adjusted conveniently to meet specific applications by changing the microstructure of the copolymers via different polymerization routes.

Effects of rapid thermal annealing on crystallinity and Sn surface segregation of Ge1-xSnx films on Si (100) and Si (111)

Germanium-tin films with rather high Sn content （28.04% and 29.61%） are deposited directly on Si （100） and Si （111） substrates by magnetron sputtering. The mechanism of the effect of rapid thermal annealing on the Sn surface segregation of Ge1-xSnx films is investigated by x-ray photoelectron spectroscopy （XPS） and atomic force microscopy （AFM）. The x-ray diffraction （XRD） is also performed to determine the crystallinities of the Ge1-xSnx films. The experimental results indicate that root mean square （RMS） values of the annealed samples are comparatively small and have no noticeable changes for the as-grown sample when annealing temperature is below 400℃. The diameter of the Sn three-dimensional （3D） island becomes larger than that of an as-grown sample when the annealing temperature is 700℃. In addition, the Sn surface composition decreases when annealing temperature ranges from 400℃ to 700℃. However, Sn bulk compositions in samples A and B are kept almost unchanged when the annealing temperature is below 600℃. The present investigation demonstrates that the crystallinity of Ge1-xSnx/Si （111） has no obvious advantage over that of Ge1-xSnx/Si （100） and the selection of Si （111） substrate is an effective method to improve the surface morphologies of Ge1-xSnx films. We also find that more severe Sn surface segregation occurs in the Ge1-xSnx/Si （111） sample during annealing than in the Ge1-xSnx/Si （100） sample.

EFFECT OF CRYSTALLINITY ON POLARIZATION FATIGUE OF FERROELECTRIC P(VDF-TrFE)COPOLYMER FILMS

The dependence of polarization fatigue on crystallinity of vinylidene fluoride and trifluoroethylene copolymer films was studied.Experimental data indicated that the higher the crystallinity of the film was,the slower the fatigue rate of the film became.A possible explanation was put forward,and it was regarded that the space charges,trapped at the boundaries of crystallites and/or captured by the defects lying both in amorphous and crystalline phases,should make the major contribution to polarization fatig...

Effect of Crystallinity on Electrochemical Insertion/Extraction of Li in Transition Metal Oxides Part I: LiMn_2O_4 and LiCo_(0.5)Ni_(0.5)O_2

Electrochemical insertion/extraction of Li on cathode materials of spinel type LiMn2O4 and ordered rock-salt type LiCo0.5 Ni0.5O2 was measured on samples of which structures were well characterized. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materiaIs on electrochemical Li insertion/extraction performance was discussed. These two transition metal oxides belong to onegroup that the crystallinity of these oxides affects to the performance.

Controlled WS_(2) crystallinity effectively dominating sodium storage performance

WS2 exhibits tremendous potentials for Na-ions storage owing to high capacity(433 mAh g^(-1)). Nevertheless, WS2 layered structure is often exfoliated with rapid capacity decay and sluggish reaction kinetics.In this work, WS2 nanosheets with different crystallinities are controlled by different synthesis methods.The high crystallinity WS2 exhibits high degree of interlayer order and strong interlayer force. It exhibits superior electrochemical properties, at the current density of 200 mA g^(-1) after 300 cycles with reversible capacity of 471 mAh g^(-1). Even at 5.0 A g^(-1), the capacities can still arrive at 240 mAh g^(-1) after 250 cycles, exhibiting stable cycling performance. Further electrochemical research finds that the high degree of interlayer order of layered WS2 structure can perform highly conducive Na+insertion/extraction with greatly improved contribution of intercalation capacity. Moreover, the strong interlayer force can effectively restrain the exfoliating of the WS2 nanosheets, guaranteeing the stability of the structure. Combining the above result reveals that controlling the order and force of the interlayer is an effective way to enhance the electrochemical properties of WS2 as SIBs anode materials. This work can provide new insight for inhibiting the exfoliation of layered compounds to pursue excellent electrochemical performance in Na-ion storage systems.

Improving the performance of polymer solar cells by adjusting the crystallinity and nanoscale phase separation

In this paper, we report a high-perfornmnce P3HT/PCBM bulk-heterojunction solar cell with a power conversion efficiency of 4.85% fabricated by adjusting the polymer crystallinity and nanoscale phase separation using an ultrasonic irradiation mixing approach for the polymer. The grazing incidence X-ray diffraction, UV/Vis spectroscopic, and atomic force microscopic measurement results for the P3HT/PCBM blend films reveal that the P3HT/PCBM film fabricated by ultrasonic irradiation mixing of the P3HT and PCBM solutions for 10 min has a higher degree of crystallinity, a higher absorption efficiency, and better phase separation, which together account for the higher charge transport properties and photovoltaic cell performance.

DETERMINATION OF DEGREE OF CRYSTALLINITY OF NYLON 1212 BY WIDE-ANGLE X-RAY DIFFRACTION

Based on the X-ray scattering intensity theory and using the approximate expression for the atomic scattering factor, the correction factors for three crystalline peaks and an amorphous peak of Nylon 1212 were calculated and the formula of degree of crystallinity of Nylon 1212 was derived by a graphic multipeak resolution method. The degree of crystallinity calculated from the WAXD method is compatible with those obtained by density and calorimetry methods.

Effect of Crystallinity on Electrochemical Insertion/Extraction of Li in Transition Metal Oxides Part Ⅱ: TiO_2, V_2O_5 and MoO_3

Electrochemical insertion/extraction of Li on cathode materials of anatase type TiO_2, quasilayered structure V_2O_5 and layered structure MoO_3 was measured on samples of which structures were well characterized and showed a wide range of crystallinity. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materials on electrochemical Li insertion/extraction pedermance was discussed. These three transition metal oxides were classified as one group on the basis of whether the crystallinity of these oxides affects to the performance or not; LiMn_2O_4 and LiCo_(0.5)O_2 belongs to the former group and TiO_2, V_2O_5 and MoO_3 to the latter.

Study of the Relative Variations of the Thermal Properties and Crystallinity of Blends (PP/EPR)/Calcium Carbonate

The objective of this paper is to investigate the relative variations of the constants of the thermal properties and the degree of crystallinity of the mixtures (PP/EPR)/Calcium carbonates elaborated with the Micro Bivis. We have strengthened the basic copolymer PP/EPR of a low level (5%) by three calcium carbonates models socal312, socal322v, Winnofil spm. We then subjected the different mixtures obtained, two cycles of a thermal loading under differential scanning calorimetry DSC. We finally focused on the thermal properties of isotactic polypropylene (TfP, TcP, ΔHfP, ΔHcP) and we calculated the degree of crystallinity of the mixtures. Reducing the energy cost of implementing mixtures is one of the objectives of this work. We quantified the relative variations of the above properties with those of the base copolymer. It shows that at a low loading rate of calcium carbonate, there is a decrease in the enthalpies of crystallization during the second exothermic cycle, with values that can reach 5.53 J/gPP for the basic copolymer PP/EPR. During the second endothermic cycle, there is an overall increase in isotactic polypropylene melting temperature values for all the blends as well as for the basic copolymer PP/EPR. There is evidence that calcium carbonates are useful for lowering the melting energy of isotactic polypropylene, even at a low loading rate for the majority. The number of endothermic cycles accentuates this phenomenon which is linked to the presence in our composites, of a so-called confined amorphous phase.

Hydrothermal Formation of Lath-Shaped Trioctahedral Smectite with High Crystallinity

Lath-shaped and highly crystalline trioctahedral smectites were synthesized under hydrothermal conditions. The quenched glasses with stoichiometrically dehydrated Na-smectite compositions were treated at （a） 500℃ and 100 MPa for 1 and 11 days; and （b） 300℃ and 100 MPa for 7 days. The crystallinity and particle size of products were dependent on the chemical composition of the starting glass, synthetic temperature and duration of hydrothermal treatment. The high structural ordering and large dimensions of the products were confirmed from the sharpness of XRD peaks; and hydration behavior under controlled relative humidity. Transmission electron microscopy was also performed for the characterization of the particle size of product. Particle sizes vary from ca. 10 nm to a few pm by changing the chemical compositions of the starting materials. The product with the highest structural ordering and largest dimension was obtained from Nao.33（Mg1.83Al0.67）Si4O11 glass treated at 500℃ and 100 MPa for 1 day. The obtained results also confirmed the metastability and compositional dependency in the formation of highly crystalline trioctahedral smectite at hydrothermal conditions.

Formation Mechanism of Impure Phases and Crystallinity Investigation of YAG Powders Synthesized via the Co-precipitation Method

We investigated the impure phase problem and summarized its two formation mechanisms of YAG powders synthesized via the co-precipitation method.The ions loss problem caused by high concentration reaction solution in the titration process was emphatically studied,and the corresponding thermodynamic explanation was carried out.In addition,influence of powder crystallinity and its new qualitative and quantitative standards were studied.One reason of impure phase is the local nonuniform mixture of Y and Al elements in precursor,which easily causes intermediate phases during calcination and difficulty of high pure powders at low temperatures.The other reason is the precipitation dissolution during titration and then the Y^(3+)/Al^(3+) loss,caused by high concentration of reaction solution.The powder crystallinity can be promoted by increasing calcination temperature or holding time of precursor.Besides the routine XRD method,the TEM-EDX method should be also introduced to directly determine the quality of crystallinity.