Chloride-based solid electrolytes are considered interesting candidates for catholytes in all-solid-state batteries due to their high electrochemical stability, which allows the use of high-voltage cathodes without protective coatings. Aliovalent Zr(iv) substitution is a widely applicable strategy to increase the ionic conductivity of Li₃M(iii)Cl₆ solid electrolytes. In this study, we investigate how Zr(iv) substitution affects the structure and ion conduction in Li_3−xIn_1−xZr_xCl₆ (0 ≤ x ≤ 0.5). Rietveld refinement using both X-ray and neutron diffraction is used to make a structural model based on two sets of scattering contrasts. AC-impedance measurements and solid-state NMR relaxometry measurements at multiple Larmor frequencies are used to study the Li-ion dynamics. In this manner the diffusion mechanism and its correlation with the structure are explored and compared to previous studies, advancing the understanding of these complex and difficult to characterize materials. It is found that the diffusion in Li₃InCl₆ is most likely anisotropic considering the crystal structure and two distinct jump processes found by solid-state NMR. Zr-substitution improves ionic conductivity by tuning the charge carrier concentration, accompanied by small changes in the crystal structure which affect ion transport on short timescales, likely reducing the anisotropy.

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The development of commercial solid-state batteries has to date been hindered by the individual limitations of inorganic and organic solid electrolytes, motivating hybrid concepts. However, the room-temperature conductivity of hybrid solid electrolytes is still insufficient to support the required battery performance. A key challenge is to assess the Li-ion transport over the inorganic and organic interfaces and relate this to surface chemistry. Here we study the interphase structure and the Li-ion transport across the interface of hybrid solid electrolytes using solid-state nuclear magnetic resonance spectroscopy. In a hybrid solid polyethylene oxide polymer–inorganic electrolyte, we introduce two representative types of ionic liquid that have different miscibilities with the polymer. The poorly miscible ionic liquid wets the polymer–inorganic interface and increases the local polarizability. This lowers the diffusional barrier, resulting in an overall room-temperature conductivity of 2.47 × 10⁻⁴ S cm⁻¹. A critical current density of 0.25 mA cm⁻² versus a Li-metal anode shows improved stability, allowing cycling of a LiFePO₄–Li-metal solid-state cell at room temperature with a Coulombic efficiency of 99.9%. Tailoring the local interface environment between the inorganic and organic solid electrolyte components in hybrid solid electrolytes seems to be a viable route towards designing highly conducting hybrid solid electrolytes.

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Indium phosphide quantum dots are the main alternative for toxic and restricted Cd-based quantum dots for lighting and display applications, but in the absence of protecting ZnSe and/or ZnS shells, InP quantum dots suffer from low photoluminescence quantum yields. Traditionally, HF treatments have been used to improve the quantum yield of InP to ~50%, but these treatments are dangerous and not well understood. Here, we develop a postsynthetic treatment that forms HF in situ from benzoyl fluoride, which can be used to strongly increase the quantum yield of InP core-only quantum dots. This treatment is water-free and can be performed safely. Simultaneous addition of the z-type ligand ZnCl2 increases the photoluminescence quantum yield up to 85%. Structural analysis via XPS as well as solid state and solution NMR measurements shows that the in situ generated HF leads to a surface passivation by indium fluoride z-type ligands and removes polyphosphates, but not PO3 and PO4 species from the InP surface. With DFT calculations it is shown that InP QDs can be trap-free even when PO3 and PO4 species are present on the surface. These results show that both polyphosphate removal and z-type passivation are necessary to obtain high quantum yields in InP core-only quantum dots. They further show that core-only InP QDs can achieve photoluminescence quantum yields rivalling those of InP/ZnSe/ZnS core/shell/shell QDs and the best core-only II-VI QDs.

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The development of high-performance all-solid-state batteries relies on charge transport in solid electrolytes, where transport across grain boundaries often limits their bulk conductivity. The argyrodite Li ₆ PS ₅ X (X = Cl, Br) solid electrolyte has a high conductivity; however, macroscopic diffusion in this material involves complex jump processes, which leads to an underestimation of the activation energy. Using a comprehensive frequency- and temperature-dependent analysis of the spin-lattice relaxation rates, a complete estimation of Li self-diffusion is demonstrated. Another experimental challenge is quantifying the impact of grain boundaries on the total bulk conductivity. Li ₆ PS ₅ Cl and Li ₆ PS ₅ Br have identical crystalline structures, but with ₆ Li MAS NMR, their resonance peaks have different chemical shifts. Exploiting this with two-dimensional ₆ Li- ₆ Li exchange NMR on a mixture of Li ₆ PS ₅ Br and Li ₆ PS ₅ Cl, we observe Li exchange between particles of these two materials across grain boundaries, allowing direct and unambiguous quantification of this often limiting process in solid-state electrolytes.

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The high Li-ion conductivity of the Li₇P₃S₁₁ sulfide-based solid electrolyte makes it a promising candidate for all-solid-state lithium batteries. The Li-ion transport over electrode-electrolyte and electrolyte-electrolyte interfaces, vital for the performance of solid-state batteries, is investigated by impedance spectroscopy and solid-state NMR experiments. An all-solid-state Li-ion battery is assembled with the Li₇P₃S₁₁ electrolyte, nano-Li₂S cathode and Li-In foil anode, showing a relatively large initial discharge capacity of 1139.5 mAh/g at a current density of 0.064 mA/cm² retaining 850.0 mAh/g after 30 cycles. Electrochemical impedance spectroscopy suggests that the decrease in capacity over cycling is due to the increased interfacial resistance between the electrode and the electrolyte. 1D exchange ⁷Li NMR quantifies the interfacial Li-ion transport between the uncycled electrode and the electrolyte, resulting in a diffusion coefficient of 1.70(3)⋅10⁻¹⁴ cm²/s at 333 K and an energy barrier of 0.132 eV for the Li-ion transport between Li₂S cathode and Li₇P₃S₁₁ electrolyte. This indicates that the barrier for Li-ion transport over the electrode-electrolyte interface is small. However, the small diffusion coefficient for Li-ion diffusion between the Li₂S and the Li₇P₃S₁₁ suggests that these contact interfaces between electrode and electrolyte are relatively scarce, challenging the performance of these solid-state batteries.

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The increased safety associated with all-solid-state batteries using inorganic ceramic electrolytes make it a promising technology, with potential to replace current commercial battery systems. The key challenges to realize this technology are the development of new solid electrolytes with high ionic conductivity and optimization of the ionic transport pathways across the multiple phases of the battery. In this study an optimal composition of the argyrodite i.e. Li₆PS₅Cl_0.5Br_0.5 is synthesized via the mechanical milling method. This material possesses a higher bulk ionic conductivity and reduced activation energy than the single halogen doped argyrodites i.e. Li₆PS₅X (X = Cl and Br), assessed by temperature-dependent impedance spectroscopy and Nuclear Magnetic Resonance (NMR) relaxometry. A combined X-ray and neutron diffraction analysis reveals an influence of the composition and distribution of halogen atoms on the Li-ion conductivity. All-solid-state batteries fabricated using Li₂S as cathode show a high reversible capacity of 820 mAh g⁻¹ for up to 30 cycles. In addition, the Li-ion diffusion across the interface between the Li₂S cathode and Li₆PS₅Cl_0.5Br_0.5 electrolyte is probed by exchange NMR spectroscopy. It reveals that Li-ion diffusion across this interface was the main factor limiting the performance of Li₆PS₅Cl_0.5Br_0.5 in the battery, despite its high bulk ionic conductivity.

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The high Li-ion conductivity of the argyrodite Li₆PS₅Cl makes it a promising solid electrolyte candidate for all-solid-state Li-ion batteries. For future application, it is essential to identify facile synthesis procedures and to relate the synthesis conditions to the solid electrolyte material performance. Here, a simple optimized synthesis route is investigated that avoids intensive ball milling by direct annealing of the mixed precursors at 550 °C for 10 h, resulting in argyrodite Li₆PS₅Cl with a high Li-ion conductivity of up to 4.96 × 10^-3 S cm^-1 at 26.2 °C. Both the temperature-dependent alternating current impedance conductivities and solid-state NMR spin-lattice relaxation rates demonstrate that the Li₆PS₅Cl prepared under these conditions results in a higher conductivity and Li-ion mobility compared to materials prepared by the traditional mechanical milling route. The origin of the improved conductivity appears to be a combination of the optimal local Cl structure and its homogeneous distribution in the material. All-solid-state cells consisting of an 80Li₂S-20LiI cathode, the optimized Li₆PS₅Cl electrolyte, and an In anode showed a relatively good electrochemical performance with an initial discharge capacity of 662.6 mAh g^-1 when a current density of 0.13 mA cm^-2 was used, corresponding to a C-rate of approximately C/20. On direct comparison with a solid-state battery using a solid electrolyte prepared by the mechanical milling route, the battery made with the new material exhibits a higher initial discharge capacity and Coulombic efficiency at a higher current density with better cycling stability. Nevertheless, the cycling stability is limited by the electrolyte stability, which is a major concern for these types of solid-state batteries.

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Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode-electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte-electrode interface design for future all-solid-state batteries.

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A novel route to prepare highly active and stable N₂O decomposition catalysts is presented, based on Fe-exchanged beta zeolite. The procedure consists of liquid phase Fe(III) exchange at low pH. By varying the pH systematically from 3.5 to 0, using nitric acid during each Fe(III)-exchange procedure, the degree of dealumination was controlled, verified by ICP and NMR. Dealumination changes the presence of neighbouring octahedral Al sites of the Fe sites, improving the performance for this reaction. The so-obtained catalysts exhibit a remarkable enhancement in activity, for an optimal pH of 1. Further optimization by increasing the Fe content is possible. The optimal formulation showed good conversion levels, comparable to a benchmark Fe-ferrierite catalyst. The catalyst stability under tail gas conditions containing NO, O₂ and H₂O was excellent, without any appreciable activity decay during 70 h time on stream. Based on characterisation and data analysis from ICP, single pulse excitation NMR, MQ MAS NMR, N₂ physisorption, TPR(H₂) analysis and apparent activation energies, the improved catalytic performance is attributed to an increased concentration of active sites. Temperature programmed reduction experiments reveal significant changes in the Fe(III) reducibility pattern with the presence of two reduction peaks; tentatively attributed to the interaction of the Fe-oxo species with electron withdrawing extraframework AlO₆ species, causing a delayed reduction. A low-temperature peak is attributed to Fe-species exchanged on zeolitic AlO₄ sites, which are partially charged by the presence of the neighbouring extraframework AlO₆ sites. Improved mass transport phenomena due to acid leaching is ruled out. The increased activity is rationalized by an active site model, whose concentration increases by selectively washing out the distorted extraframework AlO₆ species under acidic (optimal) conditions, liberating active Fe species.

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Based on its high Li-ion conductivity, argyrodite Li6PS5Br is a promising solid electrolyte for all-solid-state batteries. However, more understanding is required on the relation between the solid electrolyte conductivity and the solid-state battery performance with the argyrodite structure, crystallinity and particle size that depend on the synthesis conditions. In the present study, this relationship is investigated using neutron and X-ray diffraction to determine the detailed structure and impedance as well as 7Li solid state NMR spectroscopy to study the Li-ion kinetics. It is found that depending on the synthesis conditions the distribution of the Br dopant over the crystallographic sites in Li6PS5Br is inhomogeneous, and that this may be responsible for a larger mobile Li-ion fraction at the interface regions in the annealed argyrodite materials. Comparing the bulk and interface properties of the differently prepared Li6PS5Br materials, it is proposed that optimal solid-state battery performance requires a different particle size for the solid electrolyte only region and the solid electrolyte in the cathode mixture. In the electrolyte region, the grain boundary resistance is minimized by annealing the argyrodite Li6PS5Br resulting in relatively large crystallites. In the cathode mixture however, additional particle size reduction of the Li6PS5Br is required to provide abundant Li6PS5Br-Li2S interfaces that reduce the resistance of this rate limiting step in Li-ion transport. Thereby the results give insight in how to improve solidstate battery performance by controlling the solid electrolyte structure. @en

Tetragonal and cubic phase Na₃PS₄ sodium electrolytes were successfully prepared by a relatively low rotation speed mechanical milling (400 rpm) route, aiming at homogeneous materials. The influence of the mechanical milling and annealing on the structure and ionic conductivity are studied by XRD and impedance spectroscopy, giving insight into the optimal mechanical synthesis conditions. Fourier analysis of the XRD data, compared to DFT based MD simulations reflects the diffusion pathway, where the simulations indicate a vacancy induced high bulk Na-ion mobility in both cubic and tetragonal phases. ²³Na solid-state NMR relaxation experiments were applied to investigate the Na-ion bulk diffusion in both the cubic and tetragonal phases, showing reasonable agreement with the MD simulation results. The MD simulations indicate that the bulk mobility of both phases may be further improved by introducing more Na vacancies. The macroscopic ionic conductivity probed by impedance spectroscopy is much smaller than that predicted by the bulk Na-ion mobility, in particular for the tetragonal phase, suggesting a large impact of amorphous phase fractions and/or grain boundaries on the macroscopic Na-ion conductivity. In particular in the less crystalline cubic phase, the amorphous fraction present as a consequence of the lower annealing temperature suggests that this phase may lead to a decrease in grain boundary resistance, which may be further exploited to improve the performance of all solid state Na-ion batteries with the Na₃PS₄ solid electrolyte.

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One of the main challenges of all-solid-state Li-ion batteries is the restricted power density due to the poor Li-ion transport between the electrodes via the electrolyte. However, to establish what diffusional process is the bottleneck for Li-ion transport requires the ability to distinguish the various processes. The present work investigates the Li-ion diffusion in argyrodite Li₆PS₅Cl, a promising electrolyte based on its high Li-ion conductivity, using a combination of ⁷Li NMR experiments and DFT based molecular dynamics simulations. This allows us to distinguish the local Li-ion mobility from the long-range Li-ion motional process, quantifying both and giving a coherent and consistent picture of the bulk diffusion in Li₆PS₅Cl. NMR exchange experiments are used to unambiguously characterize Li-ion transport over the solid electrolyte-electrode interface for the electrolyte-electrode combination Li₆PS₅Cl-Li₂S, giving unprecedented and direct quantitative insight into the impact of the interface on Li-ion charge transport in all-solid-state batteries. The limited Li-ion transport over the Li₆PS₅Cl-Li₂S interface, orders of magnitude smaller compared with that in the bulk Li₆PS₅Cl, appears to be the bottleneck for the performance of the Li₆PS₅Cl-Li₂S battery, quantifying one of the major challenges toward improved performance of all-solid-state batteries.

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Amorphous titanium oxide nanoparticles were prepared from titanium isopropoxide. In situ measurements reveal an extraordinary high capacity of 810 mAh/g on the first discharge. Upon cycling at a charge/discharge rate of 33.5 mA/g, this capacity gradually decreases to 200 mAh/g after 50 cycles. The origin of this fading was investigated using X-ray absorption spectroscopy and solid-state nuclear magnetic resonance. These measurements reveal that a large fraction of the total amount of the consumed Li atoms is due to the reaction of H2 O/OH species adsorbed at the surface to Li2 O, explaining the irreversible capacity loss. The reversible capacity of the bulk, leading to the Li0.5 TiO2 composition, does not explain the relatively large reversible capacity, implying that part of Li2 O at the TiO2 surface may be reversible. The high reversible capacity, also at large (dis)charge rates up to 3.35 A/g (10C), makes this amorphous titanium oxide material suitable as a low cost electrode material in a high power battery.@en