A Robust Anti-Thermal-Quenching Phosphor Based on Zero-Dimensional Metal Halide Rb3InCl6:xSb3.

High-power phosphor-converted white light-emitting diodes (hp-WLEDs) have been widely involved in modern society as outdoor lighting sources. In these devices, due to the Joule effect, the high applied currents cause high operation temperatures (>500 K). Under these conditions, most phosphors lose their emission, an effect known as thermal quenching (TQ). Here, we introduce a zero-dimensional (0D) metal halide, Rb3InCl6:xSb3+, as a suitable anti-TQ phosphor offering robust anti-TQ behavior up to 500 K. We ascribe this behavior of the metal halide to two factors: (1) a compensation process via thermally activated energy transfer from structural defects to emissive centers and (2) an intrinsic structural rigidity of the isolated octahedra in the 0D structure. The anti-TQ phosphor-based WLEDs can stably work at a current of 2000 mA. The low synthesis cost and nontoxic composition reported here can herald a new generation of anti-TQ phosphors for hp-WLED.

Weak-Interaction Environment in a Composite Electrolyte Enabling Ultralong-Cycling High-Voltage Solid-State Lithium Batteries.

Poly(vinylidene fluoride) (PVDF)-based solid electrolytes with a Li salt-polymer-little residual solvent configuration are promising candidates for solid-state batteries. Herein, we clarify the microstructure of PVDF-based composite electrolyte at the atomic level and demonstrate that the Li+-interaction environment determines both interfacial stability and ion-transport capability. The polymer works as a "solid diluent" and the filler realizes a uniform solvent distribution. We propose a universal strategy of constructing a weak-interaction environment by replacing the conventional N,N-dimethylformamide (DMF) solvent with the designed 2,2,2-trifluoroacetamide (TFA). The lower Li+ binding energy of TFA forms abundant aggregates to generate inorganic-rich interphases for interfacial compatibility. The weaker interactions of TFA with PVDF and filler achieve high ionic conductivity (7.0 × 10-4 S cm-1) of the electrolyte. The solid-state Li||LiNi0.8Co0.1Mn0.1O2 cells stably cycle 4900 and 3000 times with cutoff voltages of 4.3 and 4.5 V, respectively, as well as deliver superior stability at -20 to 45 °C and a high energy density of 300 Wh kg-1 in pouch cells.

Disentangling the Li-Ion transport and Boundary Phase Transition Processes in Li10 GeP2 S12 Electrolyte by In-Operando High-Pressure and High-Resolution NMR Spectroscopy.

Li-ion transport and phase transition of solid electrolytes are critical and fundamental issues governing the rate and cycling performances of solid-state batteries. In this work, in-operando high-pressure nuclear magnetic resonance (NMR) spectroscopy for the solid-state battery is developed and applied, in combination with 6 Li-tracer NMR and high-resolution NMR spectroscopy, to investigate the Li10 GeP2 S12 electrolyte under true-to-life operation conditions. The results reveal that the Li10 GeP2 S12 phase may become more disordered and a large amount of conductive metastable ß-Li3 PS4 as the glassy matrix in the electrolyte transforms into less conductive phases, mainly γ-Li3 PS4 , when high current densities (e.g., ≥0.5 mA cm-2 ) are applied to the electrolyte. The overall Li-transport also varies and shows a tendency of boundary phases and Li10 GeP2 S12 synergistic dominant conduction at high currents. Accordingly, a mechanism of structural change induced by stress variation due to the drastic morphological change during Li-In alloying at high currents, and the local Li+ diffusion coefficient discrepancy is proposed. These new findings of Li-ion transport and boundary phase transition in Li10 GeP2 S12 solid electrolyte under high-pressure and high current density are first reported and will help provide previously lacking insights into the relationship of structure and performance of Li10 GeP2 S12 .

Adjusting Rotational Behavior of Molecular Rotors by a Rational Tuning of Molecular Structure.

Many crystalline molecular rotors have been developed in the past decades. However, manipulating the rotational gesture that intrinsically controls the physical performance of materials remains a challenge. Herein, we report a series of crystalline rotors whose rotational gestures can be modulated by modifying the structures of molecular stators. In these dynamic crystals, the ox2- (ox2- = oxalate anion) behave as molecular rotators performing axial-free rotation in cavities composed of five complex cations, [MII(en)3]2+ (en = ethylenediamine). The structure of [MII(en)3]2+ that serves as a molecular stator can be tuned by varying the metal center with different ionic radii, consequently altering the chemical environment around the molecular rotator. Owing to the quasi-transverse isotropy of ox2- and multiple hydrogen-bond interactions around it, the molecular rotator exhibits unusual motional malleability, i.e., it can rotate either longitudinally in the compound of ZnII, or with a tilt angle of 42° in the compound of FeII, or even laterally in the compound of CdII. The atypical dynamic behavior demonstrated here provides a new chance for the development of exquisite crystalline molecular rotors with advanced tunable functionalities.

Polymeric Sulfur as a Li Ion Conductor.

The typical polymer electrolyte matrix has been limited to the chains consisting of -C-C- or -C-O-C- or -Si-O- backbone with different solvating groups for decades. In this work, the polymeric sulfur consisting of -(S-S)n- backbone with a high sulfur content (up to 90 wt % S) was reported for the first time. The flexible -(S-S)n- chains with high S atom density create an intense "solvating" environment for Li+ conduction, achieving an excellent Li+ conductivity of 1.69 × 10-3 S cm-1 at 80 °C. Benefiting from its unique thermoplasticity, a hot-rolling process was also developed for fabricating the poly-S membrane. The symmetric solid-state Li cell using the membrane showed a high cycling stability over 300 h. The work offers a novel platform for chemists to design new polymer electrolytes that are quite different with conventional carbon-based polymer electrolytes.

Stable Interface Chemistry and Multiple Ion Transport of Composite Electrolyte Contribute to Ultra-long Cycling Solid-State LiNi0.8 Co0.1 Mn0.1 O2 /Lithium Metal Batteries.

Severe interfacial side reactions of polymer electrolyte with LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) cathode and Li metal anode restrict the cycling performance of solid-state NCM811/Li batteries. Herein, we propose a chemically stable ceramic-polymer-anchored solvent composite electrolyte with high ionic conductivity of 6.0×10-4  S cm-1 , which enables the solid-state NCM811/Li batteries to cycle 1500 times. The Li1.4 Al0.4 Ti1.6 (PO4 )3 nanowires (LNs) can tightly anchor the essential N, N-dimethylformamide (DMF) in poly(vinylidene fluoride) (PVDF), greatly enhancing its electrochemical stability and suppressing the side reactions. We identify the ceramic-polymer-liquid multiple ion transport mechanism of the LNs-PVDF-DMF composite electrolyte by tracking the 6 Li and 7 Li substitution behavior via solid-state NMR. The stable interface chemistry and efficient ion transport of LNs-PVDF-DMF contribute to superior performances of the solid-state batteries at wide temperature range of -20-60 °C.

Polymer Electrolyte Glue: A Universal Interfacial Modification Strategy for All-Solid-State Li Batteries.

In recent years solid Li+ conductors with competitive ionic conductivity to those of liquid electrolytes have been reported. However, the incorporation of highly conductive solid electrolytes into the lithium-ion batteries is still very challenging mainly due to the high resistance existing at the solid-solid interfaces throughout the battery structure. Here, we demonstrated a universal interfacial modification strategy through coating a curable polymer-based glue electrolyte between the electrolyte and electrodes, aiming to address the poor solid-solid contact and thus decrease high interfacial resistance. The liquid glue exhibits both great wettability as well as chemical/electrochemical stability to most of the electrodes, and it can be easily solidified into a polymer electrolyte layer through a "post-curing" treatment. As a result, symmetric Li batteries with the glue modification exhibit much smaller impedance and enhanced stability upon plating/stripping cycles compared to the batteries without glue modification. The all-solid-state Li-S batteries with glue modification show significantly enhanced performances. The strategy of developing glue electrolytes to improve the electrode-electrolyte interface contact provides an alternative option for improving many other solid-state batteries.

Probing Ligand-Induced Cooperative Orbital Redistribution That Dominates Nanoscale Molecule-Surface Interactions with One-Unit-Thin TiO2 Nanosheets.

Understanding the general electronic principles underlying molecule-surface interactions at the nanoscale is crucial for revealing the processes based on chemisorption, like catalysis, surface ligation, surface fluorescence, etc. However, the electronic mechanisms of how surface states affect and even dominate the properties of nanomaterials have long remained unclear. Here, using one-unit-thin TiO2 nanosheet as a model surface platform, we find that surface ligands can competitively polarize and confine the valence 3d orbitals of surface Ti atoms from delocalized energy band states to localized chemisorption bonds, through probing the surface chemical interaction at the orbital level with near-edge X-ray absorption fine structure (NEXAFS). Such ligand-induced orbital redistributions, which are revealed by combining experimental discoveries, quantum calculations, and theoretical analysis, are cooperative with ligand coverages and can enhance the strength of chemisorption and ligation-induced surface effects on nanomaterials. The model and concept of nanoscale cooperative chemisorption reveal the general physical principle that drives the coverage-dependent ligand-induced surface effects on regulating the electronic structures, surface activity, optical properties, and chemisorption strength of nanomaterials.

P2-Na0.67 Alx Mn1-x O2 : Cost-Effective, Stable and High-Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility.

Sodium layered P2-stacking Na0.67 MnO2 materials have shown great promise for sodium-ion batteries. However, the undesired Jahn-Teller effect of the Mn4+ /Mn3+ redox couple and multiple biphasic structural transitions during charge/discharge of the materials lead to anisotropic structure expansion and rapid capacity decay. Herein, by introducing abundant Al into the transition-metal layers to decrease the number of Mn3+ , we obtain the low cost pure P2-type Na0.67 Alx Mn1-x O2 (x=0.05, 0.1 and 0.2) materials with high structural stability and promising performance. The Al-doping effect on the long/short range structural evolutions and electrochemical performances is further investigated by combining in situ synchrotron XRD and solid-state NMR techniques. Our results reveal that Al-doping alleviates the phase transformations thus giving rise to better cycling life, and leads to a larger spacing of Na+ layer thus producing a remarkable rate capability of 96 mAh g-1 at 1200 mA g-1 .

Identifying the Structural Evolution of the Sodium Ion Battery Na2 FePO4 F Cathode.

Na2 FePO4 F is a promising cathode material for Na-ion batteries owing to its relatively high discharge voltage and excellent cycling performance. Now, the long- and short-range structural evolution of Na2 FePO4 F during cycling is studied by in situ high-energy X-ray diffraction (XRD), ex situ solid-state nuclear magnetic resonance (NMR), and first-principles DFT calculations. DFT calculations suggest that the intermediate phase, Na1.5 FePO4 F, adopts the space group of P21 /c, which is a subgroup (P21 /b11, No. 14) of Pbcn (No. 60), the space group of the starting phase, Na2 FePO4 F, and this space group provides a good fit to the experimental XRD and NMR results. The two crystallographically unique Na sites in the structure of Na2 FePO4 F behave differently during cycling, where the Na ions on the Na2 site are electrochemically active while those on the Na1 site are inert. This study determines the structural evolution and the electrochemical reaction mechanisms of Na2 FePO4 F in a Na-ion battery.

Nanostructured Black Phosphorus/Ketjenblack-Multiwalled Carbon Nanotubes Composite as High Performance Anode Material for Sodium-Ion Batteries.

Sodium-ion batteries are promising alternatives to lithium-ion batteries for large-scale applications. However, the low capacity and poor rate capability of existing anodes for sodium-ion batteries are bottlenecks for future developments. Here, we report a high performance nanostructured anode material for sodium-ion batteries that is fabricated by high energy ball milling to form black phosphorus/Ketjenblack-multiwalled carbon nanotubes (BPC) composite. With this strategy, the BPC composite with a high phosphorus content (70 wt %) could deliver a very high initial Coulombic efficiency (>90%) and high specific capacity with excellent cyclability at high rate of charge/discharge (∼1700 mAh g(-1) after 100 cycles at 1.3 A g(-1) based on the mass of P). In situ electrochemical impedance spectroscopy, synchrotron high energy X-ray diffraction, ex situ small/wide-angle X-ray scattering, high resolution transmission electronic microscopy, and nuclear magnetic resonance were further used to unravel its superior sodium storage performance. The scientific findings gained in this work are expected to serve as a guide for future design on high performance anode material for sodium-ion batteries.

Amorphous Li2 O2 : Chemical Synthesis and Electrochemical Properties.

When aprotic Li-O2 batteries discharge, the product phase formed in the cathode often contains two different morphologies, that is, crystalline and amorphous Li2 O2 . The morphology of Li2 O2 impacts strongly on the electrochemical performance of Li-O2 cells in terms of energy efficiency and rate capability. Crystalline Li2 O2 is readily available and its properties have been studied in depth for Li-O2 batteries. However, little is known about the amorphous Li2 O2 because of its rarity in high purity. Herein, amorphous Li2 O2 has been synthesized by a rapid reaction of tetramethylammonium superoxide and LiClO4 in solution, and its amorphous nature has been confirmed by a range of techniques. Compared with its crystalline siblings, amorphous Li2 O2 demonstrates enhanced charge-transport properties and increased electro-oxidation kinetics, manifesting itself a desirable discharge phase for high-performance Li-O2 batteries.

Chemical Prelithiated 3D Lithiophilic/-Phobic Interlayer Enables Long-Term Li Plating/Stripping.

The up-to-date lifespan of zero-excess lithium (Li) metal batteries is limited to a few dozen cycles due to irreversible Li-ion loss caused by interfacial reactions during cycling. Herein, a chemical prelithiated composite interlayer, made of lithiophilic silver (Ag) and lithiophobic copper (Cu) in a 3D porous carbon fiber matrix, is applied on a planar Cu current collector to regulate Li plating and stripping and prevent undesired reactions. The Li-rich surface coating of lithium oxide (Li2O), lithium carboxylate (RCO2Li), lithium carbonates (ROCO2Li), and lithium hydride (LiH) is formed by soaking and directly heating the interlayer in n-butyllithium hexane solution. Although only a thin coating of ∼10 nm is created, it effectively regulates the ionic and electronic conductivity of the interlayer via these surface compounds and reduces defect sites by reactions of n-butyllithium with heteroatoms in the carbon fibers during formation. The spontaneously formed lithiophilic-lithiophobic gradient across individual carbon fiber provides homogeneous Li-ion deposition, preventing concentrated Li deposition. The porous structure of the composite interlayer eliminates the built-in stress upon Li deposition, and the anisotropically distributed carbon fibers enable uniform charge compensation. These features synergistically minimize the side reactions and compensate for Li-ion loss while cycling. The prepared zero-excess Li metal batteries could be cycled 300 times at 1.17 C with negligible capacity fading.

Synthesis and characterization of fluorinated carbon nanotubes for lithium primary batteries with high power density.

The synthesis and characterization of fluorinated carbon nanotubes have been carried out under an inert gas containing fluorine. All of the samples have been characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance ((13)C and (19)F ss-NMR) and transmission electron microscopy (TEM) techniques. The comparison of the effects of various experimental parameters on the structure of fluorinated materials allows the disclosure of the fluorination mechanism. It is shown that fluorine was intercalated into the outer part of the carbon nanotubes initially where graphene layers were coaxial within a distance of 0.60 nm. In contrast, the inner part of the carbon nanotubes was not intercalated. The electrochemical performance such as discharge capacity as a cathode for a primary lithium battery has also been investigated. The samples with a F/C ratio of 0.75 exhibited the best performance, namely high energy and power densities. The highest specific energy density and specific power density were 1147 Wh kg(-1) and 8998 W kg(-1), respectively, at a current density of 4 A g(-1).

Inhibiting Formation and Reduction of Li2 CO3 to LiCx at Grain Boundaries in Garnet Electrolytes to Prevent Li Penetration.

Poor ion and high electron transport at the grain boundaries (GBs) of ceramic electrolytes are the primary reasons for lithium filament infiltration and short-circuiting of all-solid-state lithium metal batteries (ASLMBs). Herein, it is discovered that Li2 CO3 at the GBs of Li7 La3 Zr2 O12 (LLZO) sheets is reduced to highly electron-conductive LiCx during cycling, resulting in lithium penetration of LLZO. The ionic and electronic conductivity of the GBs within LLZO can be simultaneously tuned using sintered Li3 AlF6 . The generated LiAlO2 (LAO) infusion and F-doping at the GBs of LLZO (LAO-LLZOF) significantly reduce the Li2 CO3 content and broaden the energy bandgap of LLZO, which decreases the electronic conductivity of LAO-LLZOF. LAO forms a 3D continuous ion transport network at the GB that significantly improves the total ionic conductivity. Lithium penetration within LLZO is suppressed and an all-solid-state LiFePO4 /LAO-LLZOF/Li battery stably cycled for 5500 cycles at 3 C. This work reveals the chemistry of Li2 CO3 at the LLZO GBs during cycling, presents a novel lithium penetration mechanism within garnet electrolytes, and provides an innovative method to simultaneously regulate the ion and electron transport at the GBs in garnet electrodes for advanced ASLMBs.

A dielectric electrolyte composite with high lithium-ion conductivity for high-voltage solid-state lithium metal batteries.

The ionic conductivity of composite solid-state electrolytes does not meet the application requirements of solid-state lithium (Li) metal batteries owing to the harsh space charge layer of different phases and low concentration of movable Li+. Herein, we propose a robust strategy for creating high-throughput Li+ transport pathways by coupling the ceramic dielectric and electrolyte to overcome the low ionic conductivity challenge of composite solid-state electrolytes. A highly conductive and dielectric composite solid-state electrolyte is constructed by compositing the poly(vinylidene difluoride) matrix and the BaTiO3-Li0.33La0.56TiO3-x nanowires with a side-by-side heterojunction structure (PVBL). The polarized dielectric BaTiO3 greatly promotes the dissociation of Li salt to produce more movable Li+, which locally and spontaneously transfers across the interface to coupled Li0.33La0.56TiO3-x for highly efficient transport. The BaTiO3-Li0.33La0.56TiO3-x effectively restrains the formation of the space charge layer with poly(vinylidene difluoride). These coupling effects contribute to a quite high ionic conductivity (8.2 × 10-4 S cm-1) and lithium transference number (0.57) of the PVBL at 25 °C. The PVBL also homogenizes the interfacial electric field with electrodes. The LiNi0.8Co0.1Mn0.1O2/PVBL/Li solid-state batteries stably cycle 1,500 times at a current density of 180 mA g-1, and pouch batteries also exhibit an excellent electrochemical and safety performance.

Structure and Performance of NaxMn0.85Al0.1Fe0.05O2 (0.7 ≤ x ≤ 1.0) Composite Materials for Sodium-Ion Batteries.

P2 and O3 structures are two important sodium manganese oxide phases for sodium-ion batteries; however, encounter Na-deficient and poor rate performance, respectively. Herein, a systematic study of NaxMn0.85Al0.1Fe0.05O2 (0.7 ≤ x ≤ 1.0) materials is performed by employing solid-state NMR, X-ray diffraction, and electrochemical analysis, to provide an in-depth understanding on the structure and the correlated performance for the rational design. The interlayer spacing of α-NaMnO2 broadens, and the content of distorted O3 structures (α- and ß-NaMnO2) increases with raising Na content. It is exhibited that the NaMn0.85Al0.1Fe0.05O2 composite material presents better rate and cycling performance than P2-type Na0.7Mn0.85Al0.1Fe0.05O2, delivering a capacity of 87 mAh g-1 at 5 C. Significantly, the determinants of performance are further discussed, which reveal that diffusion coefficient is probably not the decisive factor restricts the rate performance of O3 and composite materials. The phase transition relaxation and the interfacial charge transfer resistance should be seriously addressed for further improvement.

Electrochemistry of P-C Bonds in Phosphorus-Carbon Based Anode Materials.

Phosphorus-carbon anode materials for alkali-metal ion storage in rechargeable batteries can simultaneously achieve high-energy density and fast charging. The P-C-bonded structure in the phosphorus-carbon materials has been observed and acknowledged to be a critical structural feature that renders improved cycling stability and rate performance. However, the underlying mechanisms, especially the role played by P-C bonds, remain elusive. By combining computational simulations and spectroscopic characterizations, we reveal that the stability of P-C bonds is critical to the electrochemical performance. In the discharge process, P-P bonds are fragile, while the bonding state of the P-C bonds is almost unchanged since electrons were mainly received by the P atoms to form lone pairs. The preserved P-C clusters can effectively serve as a reunion center for the recovery of P-P bonds in the recharging process, leading to a moderate energy change and improved cycling reversibility and structural stability of the phosphorous for electrochemical energy storage.

Interfacial Barrier of Ion Transport in Poly(ethylene oxide)-Li7La3Zr2O12 Composite Electrolytes Illustrated by 6Li-Tracer Nuclear Magnetic Resonance Spectroscopy.

Fundamental understanding of the lithium-ion transport mechanism in polymer-inorganic composite electrolyte is crucially important for the rational design of composite electrolytes for solid-state batteries. In this work, the Li+ ion transport pathway in a model composite electrolyte of PEO containing sparsely dispersed LLZO (PEO-LLZO) was studied by an advanced characterization technique, i.e., 6Li-tracer NMR spectroscopy. By analyzing the 6Li distribution within the PEO-LLZO composite at the end of the discharge of an electrochemical cell of 6Li | PEO-LLZO | stainless steel with a fixed capacity (less than the total amount of the Li+ in the composite) at various current densities, it is found that the interfacial barrier between LLZO and PEO could cause a reduced Li+ flux through LLZO, particularly at high current densities, and therefore plays a critical role in determining the Li+ transport pathway in the composite electrolyte. This work provides an intuitive picture of Li+ ion transport in a polymer-inorganic composite electrolyte that is helpful to optimize and design better composite electrolytes.

Quasi-Solid-State Ion-Conducting Arrays Composite Electrolytes with Fast Ion Transport Vertical-Aligned Interfaces for All-Weather Practical Lithium-Metal Batteries.

The rapid improvement in the gel polymer electrolytes (GPEs) with high ionic conductivity brought it closer to practical applications in solid-state Li-metal batteries. The combination of solvent and polymer enables quasi-liquid fast ion transport in the GPEs. However, different ion transport capacity between solvent and polymer will cause local nonuniform Li+ distribution, leading to severe dendrite growth. In addition, the poor thermal stability of the solvent also limits the operating-temperature window of the electrolytes. Optimizing the ion transport environment and enhancing the thermal stability are two major challenges that hinder the application of GPEs. Here, a strategy by introducing ion-conducting arrays (ICA) is created by vertical-aligned montmorillonite into GPE. Rapid ion transport on the ICA was demonstrated by 6Li solid-state nuclear magnetic resonance and synchrotron X-ray diffraction, combined with computer simulations to visualize the transport process. Compared with conventional randomly dispersed fillers, ICA provides continuous interfaces to regulate the ion transport environment and enhances the tolerance of GPEs to extreme temperatures. Therefore, GPE/ICA exhibits high room-temperature ionic conductivity (1.08 mS cm-1) and long-term stable Li deposition/stripping cycles (> 1000 h). As a final proof, Li||GPE/ICA||LiFePO4 cells exhibit excellent cycle performance at wide temperature range (from 0 to 60 °C), which shows a promising path toward all-weather practical solid-state batteries.