Fabrication of carbon microcapsules containing silicon nanoparticles-carbon nanotubes nanocomposite by sol-gel method for anode in lithium ion battery

Carbon microcapsules containing silicon nanoparticles (Si NPs)-carbon nanotubes (CNTs) nanocomposite (Si-CNT@C) have been fabricated by a surfactant mediated sol-gel method followed by a carbonization process. Silicon nanoparticles-carbon nanotubes (Si-CNT) nanohybrids were produced by a wet-type beadsmill method. To obtain Si-CNT nanocomposites with spherical morphologies, a silica precursor (tetraethylorthosilicate, TEOS) and polymer (PMMA) mixture was employed as a structure-directing medium. Thus the Si-CNT/Silica-Polymer microspheres were prepared by an acid catalyzed sol-gel method. Then a carbon precursor such as polypyrrole (PPy) was incorporated onto the surfaces of pre-existing Si-CNT/silica-polymer to generate Si-CNT/Silica-Polymer@PPy microspheres. Subsequent thermal treatment of the precursor followed by wet etching of silica produced Si-CNT@C microcapsules. The intermediate silica/polymer must disappear during the carbonization and etching process resulting in the formation of an internal free space. The carbon precursor polymer should transform to carbon shell to encapsulate remaining Si-CNT nanocomposites. Therefore, hollow carbon microcapsules containing Si-CNT nanocomposites could be obtained (Si-CNT@C). The successful fabrication was confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). These final materials were employed for anode performance improvement in lithium ion battery. The cyclic performances of these Si-CNT@C microcapsules were measured with a lithium battery half cell tests.     

Structural originations of irreversible capacity loss from highly lithiated copper oxides

We use electrochemistry, high-energy X-ray diffraction (XRD) with pair-distribution function analysis (PDF), and density functional theory (DFT) to study the instabilities of Li₂CuO₂ at varying state of charge. Rietveld refinement of XRD patterns revealed phase evolution from pure Li₂CuO₂ body-centered orthorhombic (Immm) space group to multiphase compositions after cycling. The PDF showed CuO₄ square chains with varying packing during electrochemical cycling. Peaks in the G(r) at the Cu-O distance for delithiated, LiCuO₂, showed CuO₄ square chains with reduced ionic radius for Cu in the 3+ state. At full depth of discharge to 1.5 V, CuO was observed in fractions greater than the initial impurity level which strongly affects the reversibility of the lithiation reactions contributing to capacity loss. DFT calculations showed electron removal from Cu and O during delithiation of Li₂CuO₂.     

Physical and Electrochemical Characterization of Hydrothermal Prepared α'-NaV_2O_5 Crystals

α'-NaV2O5 was prepared by a simple hydrothermal process.X-ray diffraction confirmed the orthorhombic structure of α'-NaV2O5,with preferential growth along the (001) direction.Scanning electron microscopy showed α'-NaV2O5 was composed of flake-shaped crystals.X-ray photoelectron spectroscopy confirmed the co-existence of V4+ and V5+ in α'-NaV2O5,which results in an average V4.5+ oxidation state of α'-NaV2O5.The observed Raman bands are ascribed to different V―O vibrations.α'-NaV2O5 shows a reversible specific capacity of about 100 mA·h·g-1 between 3.5 and 1.0 V,with a good capacity retention.The good electrochemical stability of the material is attributed to its structural stability during Li+ intercalation.     

An ab initio Study on the Structural and Bonding Properties of Li_2Si_3O_7

A theoretical study on the structural and electronic properties of Li2Si3O7 is performed by using density functional theory(DFT) method.The molecular structure of the crystal and two kinds of [SiO4]-tetrahedra with different number of non-bridging oxygen(Qn) are analyzed.The structure of crystal Li2Si3O7 can be considered as a framework of corner-sharing tetrahedra.From the band structure(BS),total density of state(TDOS) and projected density of state(PDOS) of the crystal,the structures of Q3,Q4,and LiO4 tetrahedra as well as their bonding characters are presented.For lithium trisilicate,we find the bond cation-NBO(nonbridging oxygen and oxygen atoms bonding to one silicon atom only) is stronger than the bond cation-BO(bridging oxygen and oxygen atoms bonding to two silicon atoms).By analyzing the ionicity of two different types of bonds of silicon-oxygen according to the Mulliken population analysis,we also find that the Si-NBO bonds have higher ionicity than Si-BO for crystalline lithium trisilicate,which agrees with other lithium silicates.     

Electrochemical hydrogen storage in porous carbons with acidic electrolytes: Uncovering the potential

Electrochemical hydrogen storage in porous carbon materials is emerging as a cost-effective hydrogen storage and transport technology with competitive power and energy densities. The merits of electrochemical hydrogen storage using porous conductive carbon-based electrodes are reviewed. The employment of acidic electrolytes in such storage systems is compared with alkaline electrolytes. The recent innovations of a proton battery for smaller-scale electricity storage, and a proton flow reactor system for larger (grid)-scale storage and bulk export of hydrogen produced from renewable energy, are briefly described. It is argued that such systems, along with variants proposed by others, all of which rely on electrochemical hydrogen storage in porous carbons, can contribute to the search for energy storage technologies essential for the transition to a zero-emission global economy.     

Single versus poly-crystalline layered oxide cathode materials for solid-state battery applications - a short review article

The recent developments in the application of single-crystalline (SC) cathode materials in solid-state batteries are discussed in this mini-review. The characteristics of SC and poly-crystalline (PC) cathode materials are explored, with emphasis on the kinetic and mechanical properties. The critical factors influencing their performance in liquid electrolyte and solid-state battery cells are investigated. Finally, the advantages and disadvantages of both morphologies are discussed and considerations to ensure a fair comparison between SC and PC cathodes in different systems are raised.     

High Lithium Capacity MxV2O5Ay·nH2O for Rechargeable Batteries

The aqueous synthesis and electrochemical properties of nanocrystalline M_xV₂O₅A_y·nH₂O are described. It is easily and quickly prepared by precipitation from acidified vanadate solutions. M_xV₂O₅A_y·nH₂O has been characterized by X-ray powder diffraction, electron microscopy, TGA, chemical analyses, and electrochemical studies. The atomic structure is related to that of xerogel-derived V₂O₅·nH₂O. In M_xV₂O₅A_y·nH₂O, M is a cation from the starting vanadate salt and A is an anion from the mineral acid. This material exhibits high, reversible Li capacity and may be considered for use in a cathode in primary and secondary batteries. The lithium capacity of an electrode composed of M_xV₂O₅A_y·nH₂O/EPDM/carbon (88/4/8) is ∼380(mA h)/g (C/80 rate) and the energy density is ∼1000(W h)/kg (120-μm-thick cathode, 4-1.5 V, versus Li metal anode). Critical parameters identified in the synthesis of M_xV₂O₅A_y·nH₂O, with respect to achieving high Li-ion insertion capacity, are acid/vanadium ratio, starting vanadate salt, and temperature. Inclusion of carbon black in the synthesis yields a composite that maintains the high Li capacity, lowers the electrochemical-cell polarization, and preserves the lithium capacity at higher discharge rates. Li-ion coin cells, using pre-lithiated graphite anodes, exhibit electrochemical performance comparable to that of Li-metal coin cells.     

Synthesis of New Lithium Ionic Conductor Thio-LISICON—Lithium Silicon Sulfides System

The new lithium ionic conductors, thio-LISICON (LIthium SuperIonic CONductor), were found in the ternary Li₂S-SiS₂-Al₂S₃ and Li₂S-SiS₂-P₂S₅ systems. Their structures of new materials, Li_4+xSi_1−xAl_xS₄ and Li_4−xSi_1−xP_xS₄ were determined by X-ray Rietveld analysis, and the electric and electrochemical properties were studied by electronic conductivity, ac conductivity and cyclic voltammogram measurements. The structure of the host material, Li₄SiS₄ is related to the γ-Li₃PO₄-type structure, and when the Li⁺ interstitials or Li⁺ vacancies were created by the partial substitutions of Al³⁺ or P⁵⁺ for Si⁴⁺, large increases in conductivity occur. The solid solution member x=0.6 in Li_4−xSi_1−xP_xS₄ showed high conductivity of 6.4×10^-4 S cm⁻¹ at 27°C with negligible electronic conductivity. The new solid solution, Li_4−xSi_1−xP_xS₄, also has high electrochemical stability up to ∼5 V vs Li at room temperature. All-solid-state lithium cells were investigated using the Li_3.4Si_0.4P_0.6S₄ electrolyte, LiCoO₂ cathode and In anode.