Design of amphiphilic poly(vinylidene fluoride-<Emphasis Type="Italic">co</Emphasis>-hexafluoropropylene)-based gel electrolytes for high-performance lithium-ion batteries

Gel polymer electrolytes (GPE) based on electrospun polymer membranes, poly(vinylidene fluoride-co-hexafluoropropylene), grafted poly(poly(ethylene glycol) methyl ether methacrylate) (PVDF-HFP-g-PPEGMA), and poly(vinylidene difluoride-co-hexafluoropropylene) (PVDF-HFP) are prepared for lithium ion batteries by incorporating with 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI). The uniform porosity and the compatibility of blend electrospun membranes avoiding the pore blocking are beneficial to enhance the electrolyte uptakes. The GPE based on the fibrous PVDF-HFP-g-PPEGMA/PVDF-HFP activated with 1 M LiTFSI (BMITFSI) show a maximum ionic conductivity of 2.3 × 10^?3 S cm^?1 at room temperature and electrochemical stability of up to 5.2 V. The Li/GPE/LiFePO₄ cells with GPE based on PVDF-HFP-g-PPEGMA/PVDF-HFP blend electrospun membrane deliver specific capacities of 163, 141, and 125 mAh g^?1 at 0.1, 0.5, and 1C rates, respectively, and remains well after 50 cycles for each rate. Therefore, the novel GPE have been demonstrated to be suitable for lithium-ion battery applications.     

A study of the microstructure,thermal properties and wetting kinetics of Sn–3Ag–<Emphasis Type="Italic">x</Emphasis>Zn lead-free solders

Microstructure, thermal properties and wetting kinetics of Sn–3Ag–xZn solders (x = 0.4, 0.6, 0.8, 1, 2 and 4 wt%) were systematically investigated. The results indicate that a small amount of Zn (Zn wt% ≤ 1 wt%) has a rather moderate effect on the microstructure morphology of the Sn–3Ag–xZn solders. The microstructures are composed of a β-Sn phase and the mixture of Ag₃Sn and ζ-AgZn particles. However, the β-Sn phase reduces its volume fraction in the entire microstructure and the intermetallic compounds population increases with the increasing of Zn content. The microstructure is dramatically changed with a further increase in the Zn content. The γ-AgZn phase is formed in a Sn–3Ag–2Zn solder. The ε-AgZn phase is formed in a Sn–3Ag–4Zn solder. The melting temperature and the undercooling of the Sn–3Ag–xZn solder alloys decrease with the increase in Zn content, reach to a minimum value when the content of Zn is 1 wt%, and then increase with further increase in Zn content. The Sn–3Ag–1Zn demonstrates the minimum value of 228.13 °C in the melting temperature and 13.87 °C in undercooling. The wetting kinetics of the main spreading stage features the power law of R ⁿ  ~ t (n = 1), which is controlled by chemical reactions at the triple line.     

Blends of hexanoyl chitosan/epoxidized natural rubber doped with EMImTFSI

Hexanoyl chitosan soluble in THF is prepared by acyl modification of chitosan. Epoxidation natural rubber (ENR25) (25 mol%) is chosen to blend with hexanoyl chitosan. Films of hexanoyl chitosan/ENR25 blends containing lithium bis(trifluoromethanesulfonyl)imide (LiN(CF₃SO₂)₂) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) are prepared by solution casting technique. FTIR results suggested that LiN(CF₃SO₂)₂ salt interacted with hexanoyl chitosan, ENR25, and EMImTFSI. EMImTFSI interacted with hexanoyl chitosan and ENR25 to form EMIm⁺-hexanoyl chitosan and EMIm⁺-ENR25 complexes, respectively. The effect of EMImTFSI on the morphology and thermal properties of the blends is investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC), respectively. The ionic conductivity of the electrolytes is measured by electrochemical impedance spectroscopy (EIS). Upon addition of 12 wt% EMImTFSI, a maximum conductivity of 1.3 × 10^?6 S cm^?1 is achieved. Methods based on impedance spectroscopy and FTIR are employed to study the transport properties of the prepared polymer electrolytes. The ac conductivity was found to obey universal law, σ(ω)?=?σ _dc ?+?Aω ^S . The temperature dependence of exponent s is interpreted by the small polaron hopping (SPH) model.     

Ion dynamics in methylcellulose–LiBOB solid polymer electrolytes

A polymer electrolyte system comprising methylcellulose (MC) as the host polymer and lithium bis(oxalato) borate (LiBOB) as the lithium ion source has been prepared via the solution cast technique. The electrolyte with the highest conductivity of 2.79 μS cm^?1 has a composition of 75 wt% MC–25 wt% LiBOB. The mobile ion concentration (n) in this sample was estimated to be 5.70?×?10²⁰ cm^?3. A good correlation between ionic conductivity, dielectric constant, and free ion concentration has been observed. The ratio of mobile ion number density (n) at a particular temperature to the concentration n ₀ of free ions at T?=?∞ (n/n ₀) and the power law exponents (s) exhibit opposite trends when varied with salt concentration.     

Studies on structural and electrical properties of Mg<Subscript>0. 5+y</Subscript> (Zr<Subscript>2-y</Subscript>Fe<Subscript>y</Subscript>) <Subscript>2</Subscript> (PO<Subscript>4</Subscript>) <Subscript>3</Subscript> ceramic electrolytes

The sample of Mg_{0. 5+y} (Zr_1-y Fe_y) ₂ (PO₄) ₃ (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg_0.5Zr (PO₄) ₃. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe³⁺ with Zr⁴⁺ in the Mg_0.5Zr (PO₄) ₃ structure was introduced as an extrainterstitial Mg²⁺ ion in the modified structured. The compound of Mg_0.5+y (Zr_1-y Fe_y)₂(PO₄)₃ with y?=?0.4 gives a maximum conductivity value of 1.25?×?10^?5 S cm^?1 at room temperature and 7.18?×?10^?5 S cm^?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ _ac (ω)?=?σ _o ? +?Aω ^α . The charge carrier concentration and mobile ion concentration increases with increase of Fe³⁺ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg²⁺ ions.     

Substitution effects on the bulk and surface properties of (Li,Ni)Mn<Subscript>2</Subscript>O<Subscript>4</Subscript>

Manganese oxides of spinel structure, LiMn₂O₄, Li_1-x Ni _x Mn₂O₄ (0.25 ≤ x≤ 0.75), and NiMn₂O₄, were studied by EDS, XRD, SEM, magnetic (M-H, M-T), and XPS measurements. The samples were synthesized by an ultrasound-assisted sol-gel method. EDS analysis showed good agreement with the formulations of the oxides. XRD and Rietveld refinement of X-ray data indicate that all samples crystallize in the Fd3m space group characteristic of the cubic spinel structure. The a-cell parameter ranges from a = 8.2276 Å (x = 0) to a = 8.3980 Å (x = 1). SEM results showed particle agglomerates ranging in size from 2.3 μm (x = 0) down to 0.8 μm (x = 1). Hysteresis magnetization vs. applied field curves in the 5–300K range was recorded. ZFC-FC measurements indicate the presence of two magnetic paramagnetic-ferrimagnetic transitions. The experimental Curie constant was found to vary from 5 to 7.1 cm³ K mol^?1 for the range of compositions studied (0 ≤ x ≤ 1). XPS studies of these oxides revealed the presence of Ni²⁺, Mn³⁺, and Mn⁴⁺. The experimental Ni/Mn atomic ratios obtained by XPS were in good agreement with the nominal values. A linear relationship of the average oxidation state of Mn with Ni content was observed. The oxide’s cation distributions as a function of Ni content from x = 0 ?Li⁺[Mn³⁺Mn⁴⁺]O₄ to x = 1 \( {\mathrm{Ni}}_{0.35}^{2+}{\mathrm{Mn}}_{0.65}^{3+}\left[{\mathrm{Ni}}_{0.65}^{2+}\right.\left.{\mathrm{Mn}}_{1.35}^{3+}\right]{\mathrm{O}}_4 \) were proposed.     

Synthesis and characterization of Ce-doped Sm<Subscript>2</Subscript>CuO<Subscript>4 + <Emphasis Type="Italic">δ</Emphasis></Subscript> cathode for IT-SOFC applications

Single-phase solid solutions of Sm_2 ? x Ce _x CuO_4 + δ (0.05 ≤ x ≤ 0.20) with tetragonal structure are synthesized using acetate combustion followed by sintering at 1373 K for 10 h. X-ray powder diffraction and transmission electron microscopy studies confirmed the formation of solid solution in a single phase. Maximum conductivity (σ = 96.0 ± 0.5 S cm^?1 at 973 K) giving composition Sm_1.90Ce_0.10CuO₄ offers the minimum activation energy (E _a = 0.32 ± 0.004 eV) among all prepared compositions. Lowest cathode polarization resistance (R _p = 3.92 ± 0.07 Ω cm² at 973 K) and activation energy (E _a = 1.12 ± 0.03 eV) values across the measured temperature range are obtained for Sm_1.90Ce_0.10CuO₄. The impedance data fitted well to the Gerischer model indicates that a chemical-electrochemical-chemical-type reaction occurred at the mixed electronic-ionic conducting cathode.     

Green electrolytes based on dextran-chitosan blend and the effect of NH<Subscript>4</Subscript>SCN as proton provider on the electrical response studies

Dextran-chitosan blend added with ammonium thiocyanate (NH₄SCN)-based solid polymer electrolytes are prepared by solution cast method. The interaction between the components of the electrolyte is verified by Fourier transform infrared (FTIR) analysis. The blend of 40 wt% dextran-60 wt% chitosan is found to be the most amorphous ratio. The room temperature conductivity of undoped 40 wt% dextran-60 wt% chitosan blend film is identified to be (3.84?±?0.97)?×?10^?10 S cm^?1. The inclusion of 40 wt.% NH₄SCN to the polymer blend has optimized the room temperature conductivity up (1.28?±?0.43)?×?10^?4 S cm^?1. Result from X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analysis shows that the electrolyte with the highest conductivity value has the lowest degree of crystallinity (χ _c) and the glass transition temperature (T _g), respectively. Temperature-dependence of conductivity follows Arrhenius theory. From transport analysis, the conductivity is noticed to be influenced by the mobility (μ) and number density (n) of ions. Conductivity trend is further verified by field emission scanning electron microscopy (FESEM) and dielectric results.     

Zum Kernphotoeffekt am Ar40 und Ar38

Liquid Argon was irradiated with bremsstrahlung from 18 to 31 MeV endpoint energy in steps of 2 MeV. The yields of the reactions Ar⁴⁰(γ, n)+(γ, p) and Ar³⁸(γ, n) were measured by detecting the 269a and the 35d rest activity with a low-level-counter. Cross section curves for the (γ, n)-processes could be found from the yield values, and they allowed together withσ _N, σ(γ, p) andσ(γ, np) a determination ofσ(γ, 2n) and σ_γabs for Ar⁴⁰. The integrated cross section forσ(γ, n) from threshold to 33 MeV yields (200±40) MeVmb for Ar⁴⁰ and (210±40) MeVmb for Ar³⁸, the corresponding value for σ_γabs being (450±60) MeVmb for Ar⁴⁰.     

The role of zirconium oxide as nano-filler on the conductivity,morphology, and thermal stability of poly(methyl methacrylate)–poly(styrene-co-acrylonitrile)-based plasticized composite solid polymer electrolytes

The plasticized composite solid polymer electrolytes (CSPE) involving polymer blends poly(methyl methacrylate)-poly(styrene-co-acrylonitrile) (PMMA-SAN), plasticizers ethylene carbonate (EC), and propylene carbonate (PC) with lithium triflate (LiCF₃SO₃) as salt and varying concentration of composite nano-filler zirconium oxide (ZrO₂) is prepared by solution casting technique using THF as solvent. The powder X-ray diffraction (XRD) studies reveal amorphous nature of the CSPE samples. Fourier transform infrared (FT-IR) spectroscopy studies reveal interaction of Li⁺ ion with plasticizers, both C=O and OCH₃ group of the PMMA, while nitrile group of SAN is inert. AC impedance and dielectric studies reveal that the ionic conductivity (σ), dielectric constant (ε’), and dielectric loss (ε”) of the prepared CSPE samples increase with increasing content of ZrO₂ nano-filler up to 6 wt% and decrease with further additions. The temperature dependence of ionic conductivity follows Arrhenius relation and indicates ion-hopping mechanism. The sample Z2 (6 wt% ZrO₂) with relaxation time τ of 8.13?×?10^–7 s possess lowest activation energy (E_a?=?0.23 eV) and highest conductivity (2.32?×?10^–4 S cm^?1) at room temperature. Thermogravimetric analysis (TGA) reveals thermal stability of highest conducting sample Z2 up to 321 °C after complete removal of residual solvent, moisture, and its impurities. Differential scanning calorimetric (DSC) studies reveal absence of glass transition temperature (T_g) corresponding to atactic PMMA for the CSPE Z2, while isotactic PMMA component shows T_g around 70 °C, which is due to increased interaction of filler with PMMA leading to change in its tacticity. Scanning electron microscopy (SEM) analysis reveals blending of PMMA/SAN polymers and lithium triflate salt. The incorporation of nano-filler ZrO₂ leads to change in surface topology of polymer matrix. Rough surface of the CSPE Z2 leads to new pathway for ionic conduction leading to maximum ionic conductivity.     

Optimized permeation and antifouling of PVDF hybrid ultrafiltration membranes: synergistic effect of dispersion and migration for fluorinated graphene oxide

Nanoparticles may have suffered from low modification efficiency in hybrid membranes due to embedding and aggregating in polymer matrix. In order to analyze the modification mechanisms of nanoparticle migration and dispersion on the properties of hybrid membranes, we designed different F/O ratios (R _F/O ) of fluorinated graphene oxide (FGO, diameter = 1.5 ~ 17.5 μm) by carbon tetrafluoride (CF₄) plasma treatment GO for 3, 5, 10, 15, and 20 min and successfully prepared novel PVDF hybrid membranes containing FGO via the phase inversion method. After a prolonged plasma treatment, the R _F/O of FGO was enhanced sharply, indicating an increasing compatibility of FGO with the matrix, especially FGO-20 (GO treated for 20 min). FGO contents in the top layer, sublayer, and the whole of membranes were probed by X-ray photoelectron spectroscopy, energy-dispersive spectrometer, and indirect computation, respectively. In the top layer of membranes, FGO contents declined from 13.14 wt% (PVDF/GO) to 4.00 wt% (PVDF/FGO-10) and 1.96 wt% (PVDF/FGO-20) due to the reduced migration ability of FGO. It is worth mentioning that PVDF/FGO-10 membranes exhibited an excellent water flux and flux recovery rate (up to 406.90 L m^?2 h^?1 and 88.9%), which were improved by 67.3% and 14.6% and 52.5% and 24.0% compared with those of PVDF/GO and PVDF/FGO-20 membranes, respectively, although the dispersion and migration ability of FGO-10 was maintained at a moderate level. It indicated that the migration and dispersion of FGO in membranes could result in dynamic equilibrium, which played a key role in making the best use of nanomaterials to optimize membrane performance.     

Bestimmung von Moleküleigenschaften des Tl205F19 aus kombinierten Stark-Zeeman-Effekt-Messungen mit der Molekularstrahlmethode

An electric Molecular-Beam-Resonance-Spectrometer has been used to measure simultanously the Zeeman- and Starkeffect splitting of the hyperfinestructure of TlF. Electric fourpole lenses served as focusing and refocusing fields of the spectrometer. A homogenous magnetic field (Zeeman-Field) was superimposed to the electric field (Stark-Field) in the transition region of the apparatus. The observedΔm _J =±1 -transitions were induced electrically. Completely resolved spectra of Tl²⁰⁵F¹⁹ in theJ=1 rotational, andυ=0 vibrational state have been measured. The obtained quantities are: The rotational magnetic momentμ _J of Tl²⁰⁵F¹⁹ in the stateJ=1,υ=0, and the difference of the magnetic shielding (σ _1,±1?σ _1,0) of both nuclei as well as the difference of the molecular susceptibility (ξ _1,±1?ξ _1,0) in the states (J, m _J)=(1,±1) and (J, m_J)=(1, 0). The sign of the rotational magnetic moment could be determined unambigously by the influence of offdiagonal matrix elements. The numerical values for Tl²⁰⁵F¹⁹ in the stateJ=1 andυ=0 are:μ _J =?29,153(21) · 10^?6 μ _Bohr (σ _1,±1?σ _1,0)^Tl=?0,002291 (33) (σ _1,±1?σ _1,0)^F=?0,000206(9) (ξ _1,±1-ξ _1,0)=+3,02(15) · 10^?30erg/Gauß² The quantities in brackets are root-mean-square deviations in units of the last digit. From these data and the known values for the spin-rotational interaction constants a number of expressions are derived which characterise the electronic charge distribution in the molecule.     

Possible violation of the δS=δQ selection rule in leptonic decays of σ+-hyperons

We have found a possible example of the rare decayσ ⁺ →nΜ ⁺ Ν, which violatesδS=δQ. The positive decay track of theσ ⁺ comes to rest in the hydrogen bubble chamber and decays into ane ⁺. This track has all the characteristics of a stoppingΜ ⁺. The decay neutron fortuitously scatters twice, producing two recoil protons. The only other possible interpretation of the event isσ ⁺→nγ(π ⁺ →Μ ⁺ Ν), where theπ ⁺ →Μ ⁺ Ν decay produces no deflection (θ<0.1 rad) and no significant change in curvature. Using thep-wave radiative decay predictions ofBarshay et al. we calculate that the integrated branching ratio for such “accidental” events isγ(σ ⁺ →nγ(π ⁺ →Μ _stop ⁺ Ν))/γ(σ ⁺ →nπ ⁺)=1.6×10^?6. Most of the contribution to this “accidental” branching ratio comes from radiative decays where theπ ⁺ mesons have ranges less than 1 mm (p _π<20 MeV/c). If one excludes thoseΜ's with ranges less than 1.2 cm the above “accidental” branching ratio becomes 5.5×10^?7. With this figure we estimate that we should have seen 6.5×10^?2 events of this type thusfar in our experiment. The neutron momentum does not help in deciding between the two hypotheses. We therefore assign a confidence level of 7% for the radiative hypothesis. For the leptonic hypothesis we obtain an estimate of the branching ratio,γ(σ ⁺ →nΜ ⁺ Ν)/γ(σ ⁺ →nπ ⁺)=5×10^?5. If one further accepts theσ ⁺ →nπ ⁺ Ν event reported byBarbaro-Galtieri et al. and theσ ⁺ →ne ⁺ Ν event reported byNauenberg et al., one obtains theδS=?δQ leptonic branching ratio [γ(σ ⁺ →nΜ ⁺ Ν)+γ(σ ⁺ →ne ⁺ Ν)]/γ(σ ⁺ →nπ ⁺)=(4±3)×10^?5.     

Über Kristallstruktur und elektrische Eigenschaften der Wismutselenide Bi2Se2 und Bi2Se3

The properties of bismuth triselenide (Bi₂Se₃) are already known to a certain extent through the work of several authors, while it was still an open question whether there exists an individual solid phase of BiSe. Further information on this subject could be obtained by the successful growth and investigation of single crystals of both Bi₂Se₃ and Bi₂Se₂. X-ray analysis by means of goniometry, Weißenberg, Laue, and Debye-Scherrer diagrams confirmed the known crystal structure of Bi₂Se₃ (ditrigonal scalenohedral;D _3d ⁵ ?R—m; with the hexagonal axes:a=4·15 Å andc=28·55 Å, and 3 molecules per unit cell). As to Bi₂Se₂ it can be shown that it belongs to the same class but to a different space group (D _3d ¹ ?P— 1m orD _3d ³ ?P—m 1; hexagonal axes:a=4·15 Å,c=22·84 Å, unit cell: 3 molecules, if the formula Bi₂Se₂ is adopted). Common to both is a subcell with the dimensions:a′=a=4·15 Å andc′=5·71 Å. The temperature dependence of electrical conductivity and Hall coefficient was measured on several specimens having different crystal orientations. The most striking difference is the high anisotropy of Bi₂Se₃ (σ _a σ _c =10) as compared with Bi₂Se₂ (σ _a /σ _c <2). All specimens turned out to ben-type. The room temperature carrier concentration observed was:n (Bi₂Se3)=8·10¹⁸ cm^?3 andn (Bi₂Se₂)=4·10²⁰ cm^?3, the carrier mobility:μ(Bi₂Se3)=2·10³ cm²/V·s andμ(Bi₂Se₃)=20 cm²/V·s.     

Gleichzeitige Messung von Hyperfeinstruktur,Starkeffekt und Zeemaneffekt des85Rb19F mit einer Molekülstrahl-Resonanzapparatur

A molecular beam resonance apparatus with electric quadrupole lenses asA- andB-fields and with superimposed parallel electric and magnetic transition-fields was used. Molecules in different rotational statesJ, m _J are separated by theA-field. Spectra of molecules in different vibrational states are resolved by their different Starkeffect energies. By this means the following electric and magnetic properties of the molecule could be measured in the rotational stateJ=1 and vibrational statesv=0 and 1: The magnetic and electric dipole moment of the molecule, the scalar and the tensor nuclear dipole — dipole interactiond _s andd _T, the nuclear spinrotational interactionc _F andc _Rb, the nuclear quadrupole interactioneqQ, the nuclear magnetic moment μ_Rb, the anisotropy of the diamagnetic susceptibility ξ_⊥?ξ_∥, the anisotropy of the diamagnetic shielding of the external field by the electrons at the position of the nuclei σ_⊥?σ_∥. Using these quantities it was possible to calculate the quadrupole moment and a weighted quadrupole moment of the electronic charge distribution. The results are: (J=1,v=0) μ_el=8,5464 (17) debμ _J/J=?29,79(2)x10^?6 μ _B d _s/h=0,36(23) kHzd _T/h=0,69(22)kHzc _F/h=10,42(70) kHzc _Rb/h=0,479 (48) kHz.eqQ _Rb/h=?70,3410(26) MHzμ(1?σ_S)Rb=1,3474(5) μ_k (ξ⊥-ξ _∥)=12(6)×10^?30 erg/Gauß² (σ_⊥-σ∥)_Rb=?3,8(2,1)×10^?4 (σ⊥-σ _∥)_F=?2,6(3)×10^?4     

New promising bulk thermoelectrics: intermetallics,pnictides and chalcogenides

The need of alternative “green” energy sources has recently renewed the interest in thermoelectric (TE) materials, which can directly convert heat to electricity or, conversely, electric current to cooling. The thermoelectric performance of a material can be estimated by the so-called figure of merit, zT = σ α ² T/λ (α the Seebeck coefficient, σ α ² the power factor, σ and λ the electrical and thermal conductivity, respectively), that depends only on the material. In the middle 1990s the “phonon glass and electron crystal” concept was developed, which, together with a better understanding of the parameters that affect zT and the use of new synthesis methods and characterization techniques, has led to the discovery of improved bulk thermoelectric materials that start being implemented in applications. During last decades, special focus has been made on skutterudites, clathrates, half-Heusler alloys, Si_1?x Ge _x-, Bi₂Te_3- and PbTe-based materials. However, many other materials, in particular based on intermetallics, pnictides, chalcogenides, oxides, etc. are now emerging as potential advanced bulk thermoelectrics. Herein we discuss the current understanding in this field, with special emphasis on the strategies to reduce the lattice part of the thermal conductivity and maximize the power factor, and review those new potential thermoelectric bulk materials, in particular based on intermetallics, pnictides and chalcogenides. A final chapter, discussing different shaping techniques leading to bulk materials (eventually from nanostructured TE materials), is also included.     

Saturation spectra of low lying states of Nitrogen: reconciling experiment with theory

The hyperfine constants of the levels 2p ² \((^{3}\)P)3s ⁴P _J , 2p ² \((^3\)P)3p ⁴P\(^o_J\) and 2p ² \((^3\)P)3p ⁴D\(^o_J\), deduced by Jennerich et al. [Eur. Phys. J. D 40, 81 (2006)] from the observed hyperfine structures of the transitions 2p ² \((^3\)P)3s ⁴P _J \(\rightarrow\) 2p ² \((^3\)P)3p ⁴P\(^o_{J'}\) and 2p ² \((^3\)P)3s ⁴P _J \(\rightarrow\) 2p ² \((^3\)P)3p ⁴D\(^o_{J'}\) recorded by saturation spectroscopy in the near-infrared,strongly disagree with the ab initio values of Jönsson et al. [J. Phys. B: At. Mol.Opt. Phys. 43, 115006 (2010)].We propose a new interpretation of the recorded weak spectral lines. If the latter are indeed reinterpreted as crossover signals, a new set of experimental hyperfine constants is deduced, in very good agreement with the ab initio predictions.     

Polyethylene-supported poly(methyl methacrylate<Emphasis Type="Italic">-co-</Emphasis>butyl acrylate)-based novel gel polymer electrolyte for lithium ion battery

A new copolymer, poly(methyl methacrylate-co-butyl acrylate) (P(MMA-co-BA)), was synthesized by emulsion polymerization with different mass ratio of methyl methacrylate (MMA) and butyl acrylate (BA). The membranes were prepared by phase inversion and corresponding gel polymer electrolytes (GPEs) were obtained by immersing the membrane into a liquid electrolyte. In this design, the hard monomer MMA provided the copolymer with good electrolyte uptake, while the soft monomer BA provided the GPE with strong adhesion between the anode and cathode of lithium ion battery. The properties of the resulting product were investigated by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectra, scanning electron spectroscopy, linear sweep voltammetry, thermogravimetric analysis, cyclic voltammetry, electrochemical impedance spectroscopy and charge/discharge test. The results show that the obtained GPE based on P(MMA-co-BA) with the mass ratios of MMA and BA = 6:1 exhibits good conductivity (as high as 1.2 × 10^?3 S cm^?1) at room temperature and high electrochemical stability (up to 4.9 V vs. Li/Li⁺). With the application of the polyethylene (PE)-supported GPE in Li/Li(Li_0.13Ni_0.30Mn_0.57)O₂ battery, the battery presents good cyclic stability (maintaining 95.4 % of its initial discharge capacity after 50 cycles) at room temperature.     

Study on LiFe<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript>/C used as cathode materials for lithium-ion batteries with low Sm component

LiFe_1???x Sm _x PO₄/C cathode materials were synthesized though a facile hydrothermal method. Compared with high-temperature solid-phase sintering, the method can allow for the fabrication of low Sm content (2 %), a scarce and expensive rare earth element, while the presence of an optimized carbon coating with large amount of sp²-type carbon sharply increases the material’s electrochemical performance. The high-rate dischargeability at 5 C, as well as the exchange current density, can be increased by 21 and 86 %, respectively, which were attributed to the fine size and the large cell parameter a/c as much. It should be pointed out that the a/c value will be increased for the LiFePO₄ Sm-doped papered by both of the two methods, while the mechanism is different: The value c is increased for the front and the value a is decreased for the latter, respectively.     

Crystal-Physical Model of Ion Transport in Nonlinear Optical Crystals of KTiOPO<Subscript>4</Subscript>

The ionic conductivity along the principal axes a, b, and c of the unit cell of the nonlinear-optical high-resistance KTiOPO₄ single crystals (rhombic syngony, space group Pna2₁), which are as-grown and after thermal annealing in vacuum, has been investigated by the method of impedance spectroscopy. The crystals were grown from a solution-melt by the Czochralski method. The as-grown KTiOPO₄ crystals possess a quasi-one-dimensional conductivity along the crystallographic c axis, which is caused by the migration of K⁺ cations: σ_║c = 1.0 × 10^–5 S/cm at 573 K. Wherein the characteristics of the anisotropy of ionic conductivity of the crystals is equal to σ_║c/σ_║a= 3 and σ_║c/σ_║b= 24. The thermal annealing at 1000 K for 10 h in vacuum increases the magnitude of σ_║c of KTiOPO₄ by a factor of 28 and leads to an increase in the ratio σ_║c/σ_║b= 2.1 × 10³ at 573 K. A crystal-physical model of ionic transport in KTiOPO₄ crystals has been proposed.