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At least 829 records · Page 46

Improved electrical properties of free standing blend polymer for renewable energy resources

Blend polymer electrolytes are prepared for salt concentration (Ö/Li = 4) with the constant ratio (0.5 gm) of PEO and PAN using solution casting technique. The prepared free standing solid polymeric film is characterized by Field Emission Scanning Electron Microscopy (FESEM) which confirms the homogeneous distribution of dissociated salt in blend polymer matrix. After addition of salt the ionic conductivity value is found to be of the order of 7.13 × 10{sup −5} Scm{sup −1} which is three orders higher when compared with pure blend polymer films. The microscopic interaction among the polymer-ion, ion-ion has been confirmed by the Fourier Transform Infrared (FTIR) Spectroscopy. A very fine correlation has been built in the electrical conductivity and FTIR result. On the basis of above finding, a prepared free standing solid polymeric film appears to be appropriate for the energy storage/conversion device applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Influence of Magnetite Nanoparticles on the Dielectric Properties of Metal Oxide/Polymer Nanocomposites Based on Polypropylene

Structure and dielectric properties of polymer nanocomposites based on isotactic polypropylene and iron oxide (Fe{sub 3}O{sub 4}) nanoparticles are studied. Distribution of magnetite nanoparticles in a polymer matrix was studied by scanning electron microscopy (SEM, Carl Zeiss). Dielectric properties of nanocomposites were examined by means of E7-21 impedance spectrometer in the frequency range of 10{sup 2}–10{sup 6} Hz and temperature interval of 298–433 K. The frequency and temperature dependences of the dielectric permittivity ε, as well as the temperature dependence of log (ρ) were constructed. It is shown that introduction of the magnetite (Fe{sub 3}O{sub 4}) nanoparticles into a polypropylene matrix increases the dielectric permittivity of nanocomposites. An increase in the dielectric permittivity is explained by the increase in the polarization ability of nanocomposites. It is found that a decrease in the specific resistance with increasing temperature up to 318 K is associated with an increase in the ionic conductivity of nanocomposites. An increase in the resistance at temperatures higher than 358 K is due to the destruction of the crystalline phase of the polymer, as a result of which the distance between the Fe{sub 3}O{sub 4} nanoparticles increases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Role of reduced precursor and solvolytic reagent molar ratio on preparation and properties of ionogel

In the present study, ionogels have been synthesized by immobilizing IL (1-ethyl-3-methylimidazolium tetrafluoroborate) in silica gel matrices using non-aqueous route. In this process, tetraethyl orho-silane (TEOS) as a precursor to silicon dioxide and formic acid as a solvolytic gelating reagent in reduced molar ratio 1:4 were used. We find that reduced molar concentration of formic acid results the formation of ionogels having less number of closed pores (totally isolated from their neighbours), larger density and stable monolithic form. TEM and SEM measurements are used to visualize the morphology of sample and closed pores present in the sample. N{sub 2}-sorption measurement is used to measure the pore parameters of the silica matrices which shows the mesoporous structure. DSC and TGA results show the change in phase transition temperature and thermal stability of IL upon confinement in silica matrices. Moreover, ionic conductivity of bulk and confined IL is measured using impedance spectroscopy and it has been found that it increases with increasing the temperature as well as concentration of IL in ionogels. Apart from these characterization techniques, ionogels have been characterized using FTIR and fluorescence spectroscopy which exhibit the change in vibrational frequencies and fluorescence behaviour of confined IL. - Highlights: • Synthesis of stable ionogel using non-hydrolytic route with reduced precursor and solvolytic reagent molar ratio. • Ionogels are free from entrapped residual reaction product. • The ionogels synthesized with higher amount of ionic liquids show bulk liquid like electrical behaviour.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ionic ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) stabilized by the covalent Si–N bonding: First-principles calculations

The structural, elastic and electronic properties of LiSi{sub 2}N{sub 3} and its substitutions by Na, K and Rb were investigated through first-principles computations. The expansion of lattice parameters of ASi{sub 2}N{sub 3} from Li, Na, K to Rb is found to be determined by the bond angle of Si–N1–Si, which suggests a possible way to improve the lithium ionic conductivity by substitutions. ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) shows the similar elastic behaviors, while the electronic band gap gradually decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. Interestingly, the analysis of electronic structure, crystal orbital Hamiltonian populations and Bader charges shows that the covalence of Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3} phase. Among ASi{sub 2}N{sub 3} phases, there is a relatively high ionicity in NaSi{sub 2}N{sub 3}; the Si–N bond strength in [Si{sub 2}N{sub 3}]{sup −} net for KSi{sub 2}N{sub 3} and RbSi{sub 2}N{sub 3} is comparable to LiSi{sub 2}N{sub 3}, but stronger than NaSi{sub 2}N{sub 3}. - Graphic abstract: Universal trend of structural and electronic properties in alkaline metal silicon nitrides, ASi{sub 2}N{sub 3}, A=Li, Na, K and Rb. - Highlights: • Trend in structure, electronic and mechanical properties of ASi{sub 2}N{sub 3} (A=Li-Rb) were predicted. • Lattice expansion of ASi{sub 2}N{sub 3} induced by the bond angle of Si–N1–Si was found. • Calculated band gap decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. • Covalent Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3}.

36 MATERIALS SCIENCE↗

Humidity Effect on Nanoscale Electrochemistry in Solid Silver Ion Conductors and the Dual Nature of Its Locality

Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically non-local cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and non-local) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Electrospun montmorillonite modified poly(vinylidene fluoride) nanocomposite separators for lithium-ion batteries

Highlights: • Composite separators of PVDF and MMT for lithium-ion batteries were electrospun. • Thermal dimensional stability and tensile property of composite separators get improved. • Presence of montmorillonite promotes electrical properties of PVDF fibrous separators. • Batteries consisting of PVDF/MMT-5% separator achieve the best performance. - Abstract: Composite separators of poly(vinylidene fluoride) (PVDF) with different contents of montmorillonite (MMT) for Li-ion batteries have been fabricated by electrospinning. The morphology, function group, crystallinity, and mechanical properties of membranes were investigated by scanning electron microscope (SEM), Fourier Transform infrared spectra (FT-IR), differential scanning calorimetry (DSC), and tensile test, respectively. Interlayer spacing of MMT in polymer was characterized by X-ray diffraction (XRD). In addition, the results of electrochemical measurements suggest that PVDF/MMT-5% composite membrane has maximum ionic conductivity of 4.2 mS cm{sup −1}, minimum interfacial resistance of 97 Ω, and excellent electrochemical stability. The cell comprising PVDF/MMT-5% composite membrane shows higher capacity and more stable cycle performance than the one using commercial Celgard PP membrane.

36 MATERIALS SCIENCE↗

Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes

The importance of exploring new solid electrolytes for all-solid-state batteries has led to significant interest in NASICON-type materials. In this work, the Sc 3+ -substituted NASICON compositions Na 3 Sc x Zr 2– x (SiO 4 ) 2- x (PO 4 ) 1+ x (termed N3) and Na 2 Sc y Zr 2- y (SiO 4 ) 1- y (PO 4 ) 2+ y (termed N2) ( x , y = 0–1) are studied as model Na + -ion conducting electrolytes for solid-state batteries. The influence of Sc 3+ substitution on the crystal structures and local atomic environments has been characterized by powder X-ray diffraction (XRD) and neutron powder diffraction (NPD), as well as solid-state 23 Na, 31 P, and 29 Si nuclear magnetic resonance (NMR) spectroscopy. A phase transition between 295 and 473 K from monoclinic C 2/ c to rhombohedral $R\bar{3}c$ is observed for the N3 compositions, while N2 compositions crystallize in a rhombohedral $R\bar{3}c$ unit cell in this temperature range. Alternating current (AC) impedance spectroscopy, molecular dynamics (MD), and high temperature 23 Na NMR studies are in good agreement, showing that, with a higher Sc 3+ concentration, the ionic conductivity (of about 10 -4 S/cm at 473 K) decreases and the activation energy for ion diffusion increases. 23 Na NMR experiments indicate that the nature of the Na + -ion motion is two-dimensional on the local atomic scale of NMR although the long-range diffusion pathways are three-dimensional. In addition, a combination of MD, bond valence, maximum entropy/Rietveld, and van Hove correlation methods has been used to reveal that the Na + -ion diffusion in these NASICON materials is three-dimensional and that there is a continuous exchange of sodium ions between Na(1) and Na(2) sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational simulation of asymmetric phase transformation in cracked Li₇La₃Zr₂O₁₂: Variant selection and chemo-mechanical implications

Coupling between microcracks and phase transformation in ion-conducting ceramics can jointly affect mechanical responses and ion transport. In this work we investigate the cubic-to-tetragonal phase transformation in Li₇La₃Zr₂O₁₂ in the presence of a microcrack under hydrostatic loading and quantify its implications for crack-tip stress concentration and Li-ion transport using phase-field and molecular dynamics simulations. The phase transformation exhibits a strong asymmetry between hydrostatic tension and compression. Under tension, the crack edge nucleates one tetragonal variant that amplifies the crack-tip stress intensity and promotes crack opening. Under compression, the crack tip nucleates a different tetragonal variant that enhances the stress-induced crack-closure tendency. Effective Li diffusivity analysis shows faster transport degradation under compression due to accelerated transformation kinetics, exposing a trade-off between mechanical stability and ionic conductivity. These results highlight the intertwined nature of cracking, phase transformation, and ionic transport in ion-conducting oxides and provide mechanistic insights into chemo-mechanical degradation of solid electrolytes.

36 MATERIALS SCIENCE↗

Structural and electrochemical properties of PEMA with the influence of MWCNT / TiO{sub 2} filler

An attempt has been made to prepare a hybrid Nano composite polymer electrolytes (NCPES) based on Poly(ethyl methacrylate) (PEMA) doped with multiwalled carbon nanotubes (MWCNT) and Titanium oxide (TiO{sub 2}) as additives, Lithium per chlorate (LiClO{sub 4}) as ionic salt and Propylene Carbonate as plasticizer (PC) by using solvent casting technique. X-ray diffraction analysis (XRD) confirms the miscibility and amorphous nature of the prepared electrolytes. It has been found from the a.c impedance analysis that the inorganic filler reduces the bulk resistance of the electrolytes and thus ionic conductivity enhanced. A high dielectric loss value is observed for the case of doped MWCNT-PEMA in comparison with pure PEMA and doped TiO{sub 2} –PEMA membranes. Based on the study of relaxation spectra, it is found that the relaxation time decreases with increase in temperature.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Effect of Na substitution for La on Li ion conductivity of Li5La3Nb2O12 garnets by sol–gel process

Highlights: • The effect of Na substitution for La on Li ion conductivity in the Li5La3Nb2O12 solid state electrolyte is reported. • The power XRD patterns reveal that the partial substitutions of Na for La in Li{sub 5+2x}La{sub 3-x}Na{sub x}Nb{sub 2}O{sub 12} electrolytes are isostructural. • The new solid state electrolyte is very stable in potential range of −0.8 to 5.0V vs. Li/Li+. - Abstract: In this paper, the effect of Na substitution for La on Li ion conductivity in the well-known Li{sub 5}La{sub 3}Nb{sub 2}O{sub 12} parents with the cubic garnet framework prepared by sol-gel process is reported. The optimum condition is at 750 °C for 6 h in air with 10% excess lithium salt. The power XRD patterns reveal that the partial substitutions of Na for La in Li5 + 2{sub x}La{sub 3-x}Na{sub x}Nb{sub 2}O{sub 12} electrolytes are isostructural. The cubic lattice parameters decrease as the molar fractions of Na increasing. Among the Li5 + 2{sub x}La{sub 3-x}Na{sub x}Nb{sub 2}O{sub 12} compounds investigated, the Na-substituted Li{sub 6.4}La{sub 2.3}Na{sub 0.7}Nb{sub 2}O{sub 12} exhibits the highest ionic conductivity of 1.6 × 10{sup −4} S cm{sup -1} at room temperature with an activation energy of 0.41 eV. The new solid state electrolyte is very stable in potential range of −0.8 to 5.0 V vs. Li/Li{sup +}, and is also chemically stable against LiMn{sub 2}O{sub 4} and LiCoO{sub 2} compounds up to 900 °C, indicating that Li{sub 6.4}La{sub 2.3}Na{sub 0.7}Nb{sub 2}O{sub 12} is a promising solid state electrolyte for all-solid-state battery application.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Tuning Transport via Interaction Strength in Cationic Conjugated Polyelectrolytes

Tuning polymer-ion interaction strength is critical for balancing ion solvation and transport in solid polymer electrolytes for battery applications. In mixed Li + /electron conducting systems for improved battery binders, the design space is further complicated by seemingly opposing design rules for electron and ion conducting polymers. Conjugated polymers functionalized with cationic side chains have demonstrated high ionic conductivity, lithium transport, and electronic conductivity by combining long-range polymer ordering with diffuse ion interactions. Herein, we demonstrate a family of mixed conducting polythiophenes functionalized with a range of cationic side chains, namely imidazolium, trimethylammonium, and ammonium groups. The strength of ionic interactions and structure of the side chains govern lithium-selective transport, resulting in high Li + conductivity (~10 –4 S/cm at 80 °C) and electronic conductivity. The more diffuse imidazolium ion affords labile ionic interactions, resulting in higher lithium transference than the other cations studied. Electronic conductivity is also higher in the imidazolium system, stemming from the ability of the planar side chains to stack while also accommodating the bulky TFSI – counterions. Finally, these results demonstrate the importance of interaction strength in ion transport while also indicating that the physical structure of the side chain has an impact on electronic conduction. The imidazolium group strikes a balance, achieving superior properties across all metrics.

36 MATERIALS SCIENCE↗

Hybrid Li-S pouch cell with a reinforced sulfide glass solid-state electrolyte film separator

Here, in this paper, sulfide glass electrolyte powder with a nominal composition of (Li 2 S) 60 (SiS 2 ) 28 (P 2 S 5 ) 12 is hot pressed at a 330°C and 12 MPa into separator films using non-woven fiberglass reinforcement. The reinforced separator films are 93% dense, bendable, and have an ionic conductivity of 0.7 mS/cm at room temperature. When integrated into hybrid Li-S coin cells with liquid electrolyte, these reinforced glass separators blocked the parasitic polysulfide shuttle sufficiently to enable reversible cycling without LiNO 3 co-salt. Furthermore, the scalability of the reinforced glass separator technology is demonstrated by assembling and testing a hybrid single-layer pouch cell.

25 ENERGY STORAGE↗

Structural and impedance studies of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} synthesized by sol-gel method

LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} is synthesized by sol-gel method by using succinic acid as chelating agent. X-ray diffraction pattern confirms the material is spinel cubic structure with Fd3m space group. Impedance spectroscopy analysis of spinel LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} was performed under a wide frequency and temperature range of 50 Hz to 5 MHz and 303 K to 783 K respectively. The hopping of the electrons, ionic conductivity and activation energy were analyzed from the relaxation frequency of the imaginary impedance (Z”). The activation energy E{sub a} is calculated from the Arrhenius plots and it is found to be 0.3713 eV, which indicates the existence of oxygen vacancy in the material. Nyquist plot indicates the presence of grain effect in the material and suppression in the grain effect is observed with increasing temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The Key Role of Grain Boundary Dynamics in Revolutionizing the Potential of Solid Electrolytes

Solid electrolytes (SEs) have the potential to enhance the safety and performance of Li-metal batteries. However, the existence of grain boundaries in polycrystalline SEs presents a significant challenge for both ionic and electronic migration, promoting the propagation of detrimental lithium dendrites. This study compares the roles of grain boundaries in electrical properties of three distinct SEs including garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZO), argyrodite-type Li 6 PS 5 Cl (LPSC), and NASICON-type Li 1+x+y Al x (Ti,Ge) 2-x Si y P 3-y O 12 (LATP). Results demonstrate that the electronic and ionic conductivities of solid-state electrolytes are affected differently by grain boundaries, depending on the specific type of electrolyte. For instance, LLZO and LATP experience dielectric breakdown at 3.7 and 5.3 V, respectively, while LPSC does not exhibit such behavior. Here, a new chemical modification is proposed that simultaneously alters the composition of both the surface and grain boundaries of SEs, ultimately reducing electronic conductivity for the LLZO SEs. Consequently, the proposed LLZO exhibits unprecedented dendrite-free cycling stability, achieving a remarkable 12 000-h lifetime at room temperature, surpassing conventional strategies such as surface coatings in dendrite mitigation. This study highlights the significance of modifying grain boundaries to design safe and durable Li-metal batteries. It provides new insights for developing SEs that are highly resistant to dendrite formation.

36 MATERIALS SCIENCE↗

Practical Challenges and Future Perspectives of All-Solid-State Lithium-Metal Batteries

The fundamental understandings and technological innovations in lithium-ion batteries are essential for delivering high energy density, stable cyclability, and cost-effective energy storages with the growing demands in the applications of electrical vehicles and smart grid. Solid-state electrolytes (SSEs) are more promising than organic liquid electrolyte in terms of excellent safety in developing lithium-metal anode as well as other high-capacity cathode chemistries, such as sulfur and oxygen. Considerable efforts have been made to give birth to the superionic conductors with ionic conductivities higher than 10 –3 S cm –1 at room temperature. Furthermore, the high interfacial impedances from the poor compatibility of SSEs with electrodes limit their practical applications, which are discussed in this review. Furthermore, the recent advances and critical challenges for all-solid-state lithium-metal batteries based on the cathode materials of lithium-intercalation compounds, sulfur, and oxygen are overviewed, and their future developments are also prospected.

25 ENERGY STORAGE↗

Performance of electrical double layer capacitors fabricated with gel polymer electrolytes containing Li{sup +} and K{sup +}-salts: A comparison

The comparative performance of the solid-state electrical double layer capacitors (EDLCs) based on the multiwalled carbon nanotube (MWCNT) electrodes and poly (vinaylidinefluoride-co-hexafluoropropyline) (PVdF-HFP) based gel polymer electrolytes (GPEs) containing potassium and lithium salts have been studied. The room temperature ionic conductivity of the GPEs have been found to be ∼3.8×10{sup −3} and 5.9×10{sup −3} S cm{sup −1} for lithium and potassium based systems. The performance of EDLC cells studied by impedance spectroscopy, cyclic voltammetry and constant current charge-discharge techniques, indicate that the EDLC with potassium salt containing GPE shows excellent performance almost equivalent to the EDLC with Li-salt-based GPE.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

OVERVIEW OF ENHANCED HANFORD SINGLE-SHELL TANK (SST) INTEGRITY PROJECT - 12128

To improve the understanding of the single-shell tanks integrity, Washington River Protection Solutions, LLC, the USDOE Hanford Site tank contractor, developed an enhanced Single-Shell Tank (SST) Integrity Project in 2009. An expert panel on SST integrity, consisting of various subject matters experts in industry and academia, was created to provide recommendations supporting the development of the project. This panel developed 33 recommendations in four main areas of interest: structural integrity, liner degradation, leak integrity and prevention, and mitigation of contamination migration, Seventeen of these recommendations were used to develop the basis for the M-45-10-1 Change Package for the Hanford Federal Agreement and Compliance Order, which is also known as the Tri-Party Agreement. The change package identified two phases of work for SST integrity. The initial phase has been focused on efforts to envelope the integrity of the tanks. The initial phase was divided into two primary areas of investigation: structural integrity and leak integrity. If necessary based on the outcome from the initial work, a second phase would be focused on further definition of the integrity of the concrete and liners. Combined these two phases are designed to support the formal integrity assessment of the Hanford SSTs in 2018 by Independent Qualified Registered Engineer. The work to further define the DOE's understanding of the structural integrity SSTs involves preparing a modern Analysis of Record using a finite element analysis program. Structural analyses of the SSTs have been conducted since 1957, but these analyses used analog calculation, less rigorous models, or focused on individual structures. As such, an integrated understanding of all of the SSTs has not been developed to modern expectations. In support of this effort, other milestones will address the visual inspection of the tank concrete and the collection of concrete core samples from the tanks for analysis of current mechanics properties. The work on the liner leak integrity has examined the leaks from 23 tanks with liner failures. Individual leak assessments are being developed for each tank to identify the leak cause and location. Also a common cause study is being performed to take the data from individual tanks to look for trends in the failure. Supporting this work is an assessment of the leak rate from tanks at both Hanford and the Savannah River Site and a new method to locate leak sites in tank liner using ionic conductivity. A separate activity is being conducted to examine the propensity for corrosion in select single shell tanks with aggressive waste layers. The work for these two main efforts will provide the basis for the phase two planning. If the margins identified aren't sufficient to ensure the integrity through the life of the mission, phase two would focus on activities to further enhance the understanding of tank integrity. Also coincident with any phase-two work would be the integrity analysis for the tanks, which would be complete in 2018. With delays in the completion of waste treatment facilities at Hanford, greater reliance on safe, continued storage of waste in the single shell tanks is increased in importance. The goal of integrity assessment would provide basis to continue SST activities till the end of the treatment mission.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Structural and electrical study of ZrO{sub 2} nanoparticles modified with surfactants

Zirconia ceramic is one of the most investigated materials for its outstanding mechanical properties and ionic conduction properties, due to its high oxygen ion conduction. In order to achieve novel properties of zirconia nanoparticles, nanoparticles of zirconia are modified by using two different surfactants (SDS and CTAB) were prepared by in-situ method using zirconia/surfactant dispersions. Zirconia nanoparticles with surfactant (SDS or CTAB) were synthesized by hydrothermal method. The structural and optical properties of Zirconia/surfactant nanoparticles were investigated comprehensively by X-Ray diffraction (XRD), and electrical measurements. XRD highlights the crystalline behavior of nanoparticles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗