Effect of LiTFSI and LiFSI on Cycling Performance of Lithium Metal Batteries Using Thermoplastic Polyurethane/Halloysite Nanotubes Solid Electrolyte

All-solid-state lithium batteries(ASSLB) are promising candidates for next-generation energy storage devices.Nevertheless,the large-scale commercial application of high energy density AS S LB with the polymer electrolyte still faces challenges.In this study,a thin solid polymer composite electrolyte(SPCE) is prepared through a facile and cost-effective strategy with an infiltration of thermoplastic polyurethane(TPU),lithium salt(LiTFSI or LiFSI),and halloysite nanotubes(HNTs) in a porous framework of polyethylene separator(PE)(TPU-HNTs-LiTFSI-PE or TPU-HNTs-LiFSI-PE).The composition,electrochemical performance,and especially the effect of anions(TFSI~-and FSI~-) on cycling performance are investigated.The results reveal that the flexible TPU-HNTs-LiTFSI-PE and TPU-HNTs-LiFSI-PE with a thickness of 34 μm exhibit wide electrochemical windows of 4.9 and 5.1 V(vs.Li+/Li) at 60℃,respectively.Reduction in FSI~-tends to form more LiF and sulfur compounds at the interface between TPU-HNTs-LiFSI-PE and Li metal anode,thus enhancing the interfacial stability.As a result,cell composed of TPU-HNTs-LiFSI-PE exhibits a smaller increase in interfacial resistance of solid electrolyte interphase(SEI) with a distinct decrease in charge-transfer resistance during cycling.Li|Li symmetric cell with TPU-HNTs-LiFSI-PE could keep its stable overpotential profile for nearly 1300 h with a low hysteresis of approximately39 mV at a current density of 0.1 mA cm~(-2),while a sudden voltage rise with internal cell impedance-surge signals was observed within 600 h for cell composed of TPU-HNTs-LiTFSI-PE.The initial capacities of NCMITPU-HNTs-LiTFSIPEILi and NCMITPU-HNTs-LiFSI-PEILi cells were 149 and 114 mAh g~(-1),with capacity retention rates of 83.52% and89.99% after 300 cycles at 0.5 C,respectively.This study provides a valuable guideline for designing flexible SPCE,which shows great application prospect in the practice of ASSLB.     

Enhancing the dehydrogenation properties of LiAlH4 using K2NiF6 as additive

Lithium alanate (LiAlH₄) is a material that can be potentially used for solid-state hydrogen storage due to its high hydrogen content (10.5 wt%). Nevertheless, a high desorption temperature, slow desorption kinetic, and irreversibility have restricted the application of LiAlH₄ as a solid-state hydrogen storage material. Hence, to lower the decomposition temperature and to boost the dehydrogenation kinetic, in this study, we applied K₂NiF₆ as an additive to LiAlH₄. The addition of K₂NiF₆ showed an excellent improvement of the LiAlH₄ dehydrogenation properties. After adding 10 wt% K₂NiF₆, the initial decomposition temperature of LiAlH₄ within the first two dehydrogenation steps was lowered to 90 °C and 156 °C, respectively, that is 50 °C and 27 °C lower than that of the аs-milled LiAlH₄. In terms of dehydrogenation kinetics, the dehydrogenation rate of K₂NiF₆-doped LiAlH₄ sample was significantly higher as compared to аs-milled LiAlH₄. The K₂NiF₆-doped LiAlH₄ sample can release 3.07 wt% hydrogen within 90 min, while the milled LiAlH₄ merely release 0.19 wt% hydrogen during the same period. According to the Arrhenius plot, the apparent activation energies for the desorption process of K₂NiF₆-doped LiAlH₄ are 75.0 kJ/mol for the first stage and 88.0 kJ/mol for the second stage. These activation energies are lower compared to the undoped LiAlH₄. The morphology study showed that the LiAlH₄ particles become smaller and less agglomerated when K₂NiF₆ is added. The in situ formation of new phases of AlNi and LiF during the dehydrogenation process, as well as a reduction in particle size, is believed to be essential contributors in improving the LiAlH₄ dehydrogenation characteristics.     

Effect of heat treatment on the roughness and mechanical properties of dental lithium disilicate glass-ceramics

In dental clinics, it is common to perform small fitting adjustments in dentures using a micro-grinding tool after testing them in the patient's mouth. This procedure increases local roughness and can lead to formation of microcracks on the prosthesis surface. This study aimed to investigate the benefits of a post-finishing heat treatment to surface roughness and crack healing and its effect on the flexural strength of lithium disilicate (LD) dental glass-ceramics. Commercially available lithium metasilicate, Li₂SiO₃, samples were heat treated at 840 °C for 7 min to induce the phase transformation into LD, Li₂Si₂O₅. The LD samples were characterized by X-ray Diffraction, Scanning Electron Microscopy, Vickers hardness, Young’s modulus, and fracture toughness. One of the surfaces of the LD samples was sanded aiming to simulate the denture fitting adjustments performed in the dentist’s laboratory, generating a rough surface, Group 1. Half of the LD samples had their biaxial flexural strength evaluated by the piston-on-three-ball test (P–3B) and the other half were submitted to a second short-term heat treatment (840 °C - 5 min), Group 2, and later assessed by the P–3B. Roughness parameters in both groups were measured by 3D optical profilometry. After the crystallization heat treatment, formation of elongated LD crystals, Li₂Si₂O₅, 35% amorphous phase, and residual Li₃PO₄ was observed. In addition, the following mechanical property values were obtained: Vickers hardness = 5.8 ± 0.1 GPa, fracture toughness = 2.2 ± 0.1 MPa m^1/2, and Young’s modulus = 100.3 ± 0.3 GPa. The samples in Group 1 showed bending strength of 206 ± 30 MPa and the following roughness parameters: Ra = 0.45 ± 0.16 μm, Rz = 22.7 ± 6.7 μm, and PV = 27.7 ± 7.1 μm. In the samples in Group 2, the Ra, Rz and PV roughness parameters were 0.31 ± 0.12 μm, 5.2 ± 2.5 μm, and 9.2 ± 4.7 μm, respectively. With this decrease in roughness, the bending strength increased by 62%, with a mean value of 331 ± 59 MPa. In the need for machine finishing of LD-based glass-ceramic dental prostheses, the use of a second short-term heat treatment at 840 °C for 5 min generates considerable gains in bending strength, increasing the lifecycle of the prosthesis as a result of reduced surface roughness caused by softening of the remaining amorphous phase in the glass-ceramic. These conditions can be adapted to each chemical and crystallographic composition of the glass-ceramic under study.     

Nanograin–glass dual-phasic,elasto-flexible,fatigue-tolerant,and heat-insulating ceramic sponges at large scales

Ceramics are considered intrinsically brittle at room temperature, which is mainly attributed to the limited availability of crystallographic slips and pre-existing geometrical flaws. Moreover, the lack of flexibility has severely hindered many high-end applications of ceramic materials. Here, we produce ceramic sponges that are simultaneously ultra-light, elasto-flexible, thermally insulating, and can fully recover from large deformation with a near-zero Poisson's ratio. These spongy materials also possess superb fatigue resistance without the accumulation of damage or structural collapse for 10,000 large-scale compressive or buckling cycles. We demonstrate the exceptional flexibility is enabled by the elastic distortion of nanograin–glassy dual phase and the fiber bulking in open-cell three-dimensional structure. Moreover, these spongy materials possess superior temperature-invariant superelasticity from deep cryogenic temperatures (−196 °C) to high temperature (1500 °C). Our study not only developed mechanically reliable lightweight ceramics for numerous extreme applications, but also provided new theoretical insights into the origin of flexibility in polycrystalline ceramics.     

Sea urchin-like LiAlO2@NiCoO2 hybrid composites with core-shell structure as high-performance Li storage materials

Sea urchin-like LiAlO₂@NiCoO₂ hybrid composites with core-shell structure assembled with nanoneedles have been successfully fabricated through a facile hydrothermal route followed by a calcination procedure in N₂ for the first time. The sea urchin-like architecture with large accessible surface can offer numerous active sites for redox reaction. The synergy of two advantages has dramatically improved the electrochemical behavior in terms of specific capacity, cycle performance and rate capability, especially at high current densities. The LiAlO₂(5.0 wt%)@NiCoO₂ displays charge capacities are 1309.0 and 933.6 mAh g^?1 at 0.5 and 1A g^?1, respectively, after 400 cycles. However, the charge capacities of bare NiCoO₂ are only 562.9 and 476.7 mAh g^?1 at corresponding rates. Especially, LiAlO₂(5.0 wt%)@NiCoO₂ preserves 358.1 mAh g^?1 after 500 cycles at 2A g^?1 with a capacity retention of 74%. The superior electrochemical property is related to the sea urchin-like nature and the ingenious composition design. In addition, the DFT calculation result shows that the formed stable, well-coordinated, and metallic interface between LiAlO₂ and NiCoO₂ are very helpful for reducing the interfacial impedance and beneficial for the improved rate capability of the materials. Therefore, such LiAlO₂@NiCoO₂ composites with unique morphology demonstrate a huge potential as electrode materials for Li-ion batteries.     

Determination of optical and structural properties of lithium silicate ceramics with different ratios of Sm doped

In this study, the synthesis and luminescence characterization of Samarium (Sm³⁺) doped lithium metasilicate (Li₂SiO₃) phosphor ceramic were investigated. It was presented and discussed the results obtained on the luminescence and other optical studies such as X-ray diffraction (XRD), optical absorption and luminescence properties of Li₂SiO₃:Sm³⁺ phosphor ceramic. The Li₂SiO₃ compound was shown a characteristic phase in XRD. The doping in the lithium compound was not having a significant effect on the basic crystal structure of the material. The maximum photoluminescence (PL) emission for Sm³⁺ doped Li₂SiO₃ was observed at 554, 583, 641, 725 nm and bore resemblance to the visible region of the spectrum. The glow curves of all synthesized materials have a complex peak structure after being irradiated with a ⁹⁰Sr–⁹⁰Y beta source. In addition, the peak between 400 and 600 nm was seen in the radioluminescence (RL) spectrum because of a wide peak thought to be caused by silicate.     

Can hydrogen be the sustainable fuel for mobility in India in the global context?

This article provides a critical assessment of H₂ from the standpoint of more widespread use as a sustainable fuel for Indian mobility applications in the global context. The potential techno-economic advantages of utilizing H₂ for automobiles rather than battery electric vehicles or conventional internal combustion engine vehicles are emphasized. The present assessment demonstrates that H₂ production, storage, and distribution costs are the primary challenges, and a significant improvement is still necessary for H₂ to compete either against the internal combustion engine vehicle or the battery electric vehicle to win the race, arguably. The secondary challenges have also been demonstrated, which include the cost of the fuel cell stack and the modifications associated with internal combustion engine vehicles, as well as regulatory and safety concerns, which impede the widespread usage of H₂. It is critical that policy-making for sustainable mobility in India is possible with the aid of a National H₂ Energy Road-Map. This in turn can achieve a cost target of $0.5/kg for H₂.     

Hierarchical porous transition metal oxide nanosheets templated from waste bagasse: General synthesis and Li/Na storage performance

As a promising anode candidate, hierarchical porous transition metal oxide nanosheets (TMO-NSs) have attracted significant interest due to their various advantages of abundant active sites, high specific capacity and shortened ion/electrons transport pathways. Although the TMO-NSs have been developed in the past decades, the previous synthesis strategies have some drawbacks such as high cost, complex synthesis techniques, and the requirement of special instruments. Herein, we develop a generalized and facile biomorphic method to synthesize various controllable hierarchical porous TMO-NSs by using waste bagasse as biotemplate. Furthermore, the porosity and pore size of as-prepared hierarchical porous TMO-NSs can be adjusted by changing the precursor solution concentration. Novel hierarchical porous TMO-NSs have been successfully prepared for many ternary or binary TMO, such as NiFe₂O₄, ZnFe₂O₄, ZnMn₂O₄, NiO and ZnO. Owing to their unique nanostructure, as-synthesized hierarchical porous TMO-NSs show an excellent electrochemical performance when used as anode for Li/Na-ion batteries. We believe that various hierarchical porous TMO-NSs available from the green, economical and convenient biomorphic strategy may lead to further developments in research and application on TMO-NSs materials.     

Design of Ti4+-doped Li3V2(PO4)3/C fibers for lithium energy storage

In this work, we propose a facile approach to fabricate Ti⁴⁺-doped Li₃V₂(PO₄)₃/C (abbreviated as C-LVTP) nanofibers using an electrospinning route followed by a high temperature treatment. In this designed nanocomposite, the ultrafine LVTP dots are homogeneously dispersed into one-dimensional carbon nanofibers and the Ti⁴⁺ doping does not destroy the crystal structure of monoclinic Li₃V₂(PO₄)₃. Compared to the undoped Li₃V₂(PO₄)₃/C (abbreviated as C-LVP), the as-fabricated C-LVTP fibers present higher reversible capacity, superior high-rate capability as well as better cyclic property. Especially, the C-LVT_7%P cathode delivers not only high capacities of 187.2 and 160.3 mAh g^?1 at 0.5 and 10 C respectively, but also stable cyclic property with the reversible capacity of 135.8 mAh g^?1 at 20 C following 500-cycle spans. The good battery characteristics of C-LVT_7%P can be mainly ascribed to Ti⁴⁺ doping, which can increase the electrical conductivity and Li⁺ diffusion coefficient.     

Ion migration behavior and its interaction with sintering environment in cation conductor during flash sintering

Flash sintering has been reported in various ceramics. Nevertheless, anion and cation conductors exhibit different flash-sintering behaviors, and the interaction mechanism between the conductive species and the sintering environment has remained unclear. Herein, we report the flash-sintering phenomena of a typical cation conductor, Na₃Zr₂(SiO₄)₂(PO₄) with anode region surrounded by air and NaNO₃ environments. The results prove that the ionic behavior and joule heating distribution can be controlled by changing the electrode environment. Four possible scenarios describing the ion migration behavior and interaction with the environment are proposed for providing a guidance for controlling the ion interaction behavior during flash sintering.