Designing Advanced Electrolytes for High-Safety and Long-Lifetime Sodium-Ion Batteries via Anion-Cation Interaction Modulation.

Safety hazards caused by flammable electrolytes have been major obstacles to the practical application of sodium-ion batteries (SIBs). The adoption of nonflammable all-phosphate electrolytes can effectively improve the safety of SIBs; however, traditional low-concentration phosphate electrolytes are not compatible with carbon-based anodes. Herein, we report an anion-cation interaction modulation strategy to design low-concentration phosphate electrolytes with superior physicochemical properties. Tris(2,2,2-trifluoroethyl) phosphate (TFEP) is introduced as a cosolvent to regulate the ion-solvent-coordinated (ISC) structure through enhancing the anion-cation interactions, forming the stable anion-induced ISC (AI-ISC) structure, even at a low salt concentration (1.22 M). Through spectroscopy analyses and theoretical calculations, we reveal the underlying mechanism responsible for the stabilization of these electrolytes. Impressively, both the hard carbon (HC) anode and Na4Fe2.91(PO4)2(P2O7) (NFPP) cathode work well with the developed electrolytes. The designed phosphate electrolyte enables Ah-level HC//NFPP pouch cells with an average Coulombic efficiency (CE) of over 99.9% and a capacity retention of 84.5% after 2000 cycles. In addition, the pouch cells can operate in a wide temperature range (-20 to 60 °C) and successfully pass rigorous safety testing. This work provides new insight into the design of the electrochemically compatibility electrolyte for high-safety and long-lifetime SIBs.

Mobile Ions in Composite Solids.

Fast ion conduction in solid-state matrices constitutes the foundation for a wide spectrum of electrochemical systems that use solid electrolytes (SEs), examples of which include solid-state batteries (SSBs), solid oxide fuel cells (SOFCs), and diversified gas sensors. Mixing different solid conductors to form composite solid electrolytes (CSEs) introduces unique opportunities for SEs to possess exceptional overall performance far superior to their individual parental solids, thanks to the abundant chemistry and physics at the new interfaces thus created. In this review, we provide a comprehensive and in-depth examination of the development and understanding of CSEs for SSBs, with special focus on their physiochemical properties and mechanisms of ion transport therein. The origin of the enhanced ionic conductivity in CSEs relative to their single-phase parents is discussed in the context of defect chemistry and interfacial reactions. The models/theories for ion movement in diversified composites are critically reviewed to interrogate a general strategy to the design of novel CSEs, while properties such as mechanical strength and electrochemical stability are discussed in view of their perspective applications in lithium metal batteries and beyond. As an integral component of understanding how ions interact with their composite environments, characterization techniques to probe the ion transport kinetics across different temporal and spatial time scales are also summarized.

Distinctly different solvation behaviors of poly(N,N-diethylacrylamide) gels in water/acetone and water/DMSO mixtures.

The solvation behaviors and intermolecular interactions of a poly(N,N-diethylacrylamide) (PDEA) gel network in water/DMSO and water/acetone mixtures have been investigated by variable-temperature high-resolution 1H MAS NMR. Unlike decreasing volume phase transition temperature (VPTT) of the typical thermosensitive poly(N-isopropylacrylamide) (PNIPAM) gel induced by both acetone and DMSO in a water-rich region, distinct phase transition behaviors are revealed for the PDEA gel. That is, acetone is found to increase the VPTT of PDEA directly in the water-rich region while DMSO is also found to increase the VPTT of PDEA at a very low concentration but then decrease the VPTT as the concentration further increases. The above distinctly different VPTT shifts of PDEA are attributed to the different polymer-cosolvent interactions in water/acetone and water/DMSO systems. DMSO molecules with a strong water affinity are preferentially excluded by the PDEA gel network, and can promote the volume phase transition by favoring the collapse of the PDEA gel network, while acetone molecules preferentially adsorbed on the polymer interact with PDEA via non-specific van der Waals interaction, which favors the swollen state of the PDEA gel.

36-Nuclearity Organophosphonate-Functionalized Polyoxomolybdates: Synthesis, Characterization and Selective Catalytic Oxidation of Sulfides.

The crown-shaped 36-molybdate cluster organophosphonate-functionalized polyoxomolybdates with the highest nuclearity in organophosphonate-based polyoxometalate chemistry, (NH4 )19 Na7 H10 [Cu(H2 O)TeMo6 O21 {N(CH2 PO3 )3 }]6 ⋅31 H2 O, has been reported for the first time. The synthesized 36-molybdate cluster was characterized by routine techniques and tested as a heterogeneous catalyst for selective oxidation of sulfides with impressive catalytic and selective performances after heat treatment. High efficiency (TON=15333) was achieved in the selective oxidation of sulfides to sulfoxides, caused by the synergic effect between copper and polyoxomolybdates and the generation of the cuprous species during the heat treatment.

Dynamic mechanism of halide salts on the phase transition of protein models, poly(N-isopropylacrylamide) and poly(N,N-diethylacrylamide).

The effects of salts on protein systems are not yet fully understood. We investigated the ionic dynamics of three halide salts (NaI, NaBr, and NaCl) with two protein models, namely poly(N-isopropylacrylamide) (PNIPAM) and poly(N,N-diethylacrylamide) (PDEA), using multinuclear NMR, dispersion corrected density functional theory (DFT-D) calculations and dynamic light scattering (DLS) methods. The variation in ionic line-widths and chemical shifts induced by the polymers clearly illustrates that anions rather than cations interact directly with the polymers. From the variable temperature measurements of the NMR transverse relaxation rates of anions, which characterize the polymer-anion interaction intensities, the evolution behaviors of Cl-/Br-/I- during phase transitions are similar in each polymer system but differ between the two polymer systems. The NMR transverse relaxation rates of anions change synchronously with the phase transition of PNIPAM upon heating, but they drop rapidly and vanish about 3-4.5 °C before the phase transition of PDEA. By combining the DFT-D and DLS data, the relaxation results imply that anions escape from the interacting sites with PDEA prior to full polymer dehydration or collapse, which can be attributed to the lack of anion-NH interactions. The different dynamic evolutions of the anions in the PNIPAM and PDEA systems give us an important clue for understanding the micro-mechanism of protein folding in a complex salt aqueous solvent.

Rotational Cluster Anion Enabling Superionic Conductivity in Sodium-Rich Antiperovskite Na3OBH4.

Sodium superionic conductors are keys to develop high safety and low cost all-solid-state sodium batteries. Among developed sodium ionic conductors, antiperovskite-type ionic conductors have attracted vast interest due to their high structural tolerance and good formability. Herein, we successfully synthesize Na3OBH4 with cubic antiperovskite structure by solid-state reaction from Na2O and NaBH4. Na3OBH4 exhibits ionic conductivity of 4.4 × 10-3 S cm-1 at room temperature (1.1 × 10-2 S cm-1 at 328 K) and activation energy of 0.25 eV. The ionic conductivity is 4 orders of magnitude higher than the existing antiperovskite Na3OX (X = Cl, Br, I). It is shown that such enhancement is not only due to the specific cubic antiperovskite structure of Na3OBH4 but also because of the rotation of BH4 cluster anion. This work deepens the understanding of the antiperovskite structure and the role of cluster anions for superionic conduction.

Inhomogeneous-collapse driven micelle-vesicle transition of amphiphilic block copolymers.

Understanding the morphological transition dynamics related to the hydrophilic-hydrophobic interface has been a challenge due to the lack of an effective evaluation method. Herein, nuclear magnetic resonance spectroscopy was employed to study the morphological transition related chain collapse of poly(N,N'-diethylaminoethylmethacrylate)-b-poly(N-isopropylacrylamide) (PDEAEMA133-b-PNIPA322) and poly(N,N'-dimethylaminoethylmethacrylate)-b-poly(N-isopropylacrylamide) (PDMAEMA95-b-PNIPA228) and was proved to be a powerful technique in morphological transition mechanism studies once combined with dynamic light scattering and transmission electron microscopy. Unlike the cooperative coil collapse of two blocks in the PDMAEMA95-b-PNIPA228 alkaline solution upon heating which induces the assembly of a nanostructure (∼200 nm) with a hydrophobic core containing both collapsed PDMAEMA and PNIPA segments and a hydrophilic surface part consisting of un-shrunk PDMAEMA and PNIPA segments, PDEAEMA133-b-PNIPA322 with a low-temperature core-shell micelle structure showed a micelle-vesicle transition due to temperature-induced inhomogeneous-collapse of PNIPA. The PNIPA segments in the shell sequentially collapse outside (starting at the core-shell interface), accompanied by a gradual decrease in micelle size. Above the critical temperature, the residual hydrophilic PNIPA segments become too short to stabilize the micelle structure, the micelles then transform into vesicles of a slightly larger size, instead of micelle aggregation and precipitation as normally expected.

Preferential adsorption of the additive is not a prerequisite for cononsolvency in water-rich mixtures.

Cononsolvency of poly(N-isopropylacrylamide) (PNIPAM) gels in binary mixed solvents (water-acetone and water-DMSO) has been comparatively investigated by 1H HR-MAS NMR spectroscopy. The results demonstrate that, although the addition of both acetone and DMSO gives rise to cononsolvency behavior, PNIPAM preferentially interacts with acetone rather than DMSO in a water-rich regime, regardless of whether the temperature is above or below the volume phase transition temperature (VPTT). It suggests that the preferential adsorption of the additive cannot be deemed as a prerequisite for the cononsolvency in water-rich mixtures. The underlying molecular mechanism of cononsolvency involves a delicate balance between polymer-solvent and solvent-solvent interactions. Moreover, a new NOE-based NMR approach has been proposed to study the preferential adsorption in this work, which can be extensively adopted to study other relevant processes, including protein hydration, ligand binding, enzyme catalysis, etc.

Efficient organic dyes based on perpendicular 6,12-diphenyl substituted indolo[3,2-b]carbazole donor.

Three novel indolo[3,2-b]carbazole-based dyes have been designed and synthesized using a 6,12-diphenyl substituted indolo[3,2-b]carbazole core as a π-conjugated donor, a thiophene cyanoacrylic acid moiety as electron acceptor and anchoring group, together with triphenylamine, 3,4,5-trimethoxybenzene and bromine as a second donor group. The photophysical and electrochemical properties of the dyes have been investigated by UV spectroscopy and cyclic voltammetry (CV). Our study indicates that the second donor plays the important role of improving dye aggregation as well as tuning the photoelectronic properties. These indolo[3,2-b]carbazole based dyes show good performances with high Voc of 0.75 V, FF of 0.72, and a moderate PCE of 3.11% under AM 1.5 irradiation.

Highly mobile segments in crystalline poly(ethylene oxide)8:NaPF6 electrolytes studied by solid-state NMR spectroscopy.

Two types of high-crystallinity poly(ethylene oxide)/NaPF6 electrolytes with ethylene oxide (EO)/Na molar ratios of 8:1 and 6:1, termed as PEO8:NaPF6 and PEO6:NaPF6 with Mw = 6000 g mol(-1) were prepared, and their ionic conductivity, structure, and segmental motions were investigated and compared. PEO8:NaPF6 polymer electrolyte exhibits the room-temperature ionic conductivity 7.7 × 10(-7) S cm(-1) which is about five times higher than the PEO6:NaPF6. By variable-temperature measurements of static powder spectra and (1)H spin-lattice relaxation time in rotation frame ((1)H T1ρ), we demonstrate that crystalline segments are more highly mobile in the crystalline PEO8:NaPF6 with higher ionic conductivity than in the PEO6:NaPF6 with lower ionic conductivity. The large-angle reorientation motion of polymer segments in the PEO8:NaPF6 onsets at lower temperature (∼233 K) with a low activation energy 0.31 eV that is comparable with that of the pure PEO crystal. Whereas, the large-angle reorientation motion of polymer segments in the PEO6:NaPF6 starts around 313 K with a high activation energy of 0.91 eV. As a result of the temperature-enhanced large-angle reorientations, the (13)C static powder lineshape changes markedly from a low-temperature wide pattern with apparent principal values of chemical shift δ33 < δ22 < δ11 to a high-temperature narrow pattern of uniaxial chemical shift anisotropy δ33 > δ22 (δ11). It is suggested that the segmental motion in crystalline PEO-salt complex promotes ionic conductivity.

Preparation of Single-Helical Curdlan Hydrogel and Its Activation with Coagulation Factor G.

ß-1,3-glucans are a kind of natural polysaccharide with immunomodulatory, antitumor, and anti-inflammatory properties. Curdlan, as the simplest linear ß-1,3-glucan, possesses a variety of biological activities and thermogelation properties. However, due to the complexity and variability of the conformations of curdlan, the exact structure-activity relationship remains unclear. We prepare a chemically crosslinked curdlan hydrogel with the unique single-helical skeleton (named S gel) in 0.4 wt% NaOH at 40 °C, confirmed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). X-ray diffractometry (XRD) data show that S gel maintains the single-helical crystal structure, and the degree of crystallinity of the S gel is ~24%, which is slightly lower than that of the raw powder (~31%). Scanning electron microscopy (SEM) reveals that S gel has a continuous network structure, with large pores measuring 50-200 µm, which is consistent with its high swelling property. Using the 13C high-resolution magic angle spinning nuclear magnetic resonance (HRMAS NMR) method, we determine that most of the single-helical skeleton carbon signals in the swollen S gel are visible, suggesting that the single-helical skeleton of S gel exhibits fascinating mobility at room temperature. Finally, we reveal that the binding of S gel to coagulation Factor G from tachypleus amebocyte lysate increases and saturates at 20 µL tachypleus amebocyte lysate per mg of S gel. Our prepared S gel can avoid the transformation of curdlan conformations and retain the bioactivity of binding to coagulation Factor G, making it a valuable material for use in the food industry and the pharmaceutical field. This work deepens the understanding of the relationship between the single-helical structure and the activity of curdlan, promoting the development and application of ß-1,3-glucans.

An easy-built Halbach magnet for LF-NMR with high homogeneity using optimized target-field passive shimming method.

The aim of this work is to develop a Halbach magnet that possesses characteristics such as easy-built, low cost and high homogeneity for use in a portable low-field NMR (LF-NMR) system. Considering portability, a 4-ring Halbach magnet was designed through simulation and mechanical modelling, which was successfully constructed in a general laboratory setting. The obtained field strength (B0) was 0.169 T, with an initial homogeneity of 8204 ppm within a sphere with a diameter of 20 mm. To enhance robustness, efficiency and effectiveness of shimming, an optimized target-field passive shimming method was proposed. Subsequently, the homemade spectrometer was used to run NMR experiments on the Halbach magnet. The 1H NMR linewidths of water samples became significantly narrower after passive shimming, e.g., the linewidth of a sample with a diameter of 3 mm and a length of 3 mm reduced from 452.3 Hz (62.5 ppm) to 12.9 Hz (1.8 ppm), which was much less than 102 Hz. The NMR results demonstrate that the proposed passive shimming method can achieve high homogeneity, and the developed Halbach magnet is capable of satisfying numerous LF-NMR applications.

Low concentration electrolyte with non-solvating cosolvent enabling high-voltage lithium metal batteries.

Developing low cost, yet high-voltage electrolyte is significant to improve the energy density and practicability of lithium metal batteries (LMBs). Low concentration electrolyte has significant merits in terms of cost and viscosity; however, their poor compatibility with high-voltage LMBs hinders its applications. Here, we develop a diluted low concentration electrolyte by replacing solvating cosolvent with a non-solvating cosolvent to facilitate the interaction between BF4 - and Li+, resulting in optimized interfacial chemistry and suppressed side reaction. Thus, the high-loading Li-LiCoO2 full cells (20.4 mg cm-2) deliver outstanding cycling stability and rate performance at a cutoff voltage of 4.6 V. More impressively, a Li-LiCoO2 pouch cell achieves an energy density of more than 400 Wh kg-1 under practical conditions with thin Li (50 µm) and lean electrolyte (2.7 g Ah-1). This work provides a rational approach to design a low concentration electrolyte, which can be extended to other high voltage battery systems.

A simple and efficient method to prepare graphene by reduction of graphite oxide with sodium hydrosulfite.

Inspired by an ancient reducing method used in textile production, sodium hydrosulfite was used to reduce graphite oxide as an efficient reducing agent in our work. The reduced materials were characterized by x-ray photoelectron spectroscopy, thermogravimetric analysis, wide-angle x-ray scattering, Raman spectroscopy, solid state (13)C NMR spectroscopy and electrical conductivity measurements, respectively. The results showed that graphite oxide can be reduced with sodium hydrosulfite in a few minutes, with a degree of reduction comparable to those achieved with hydrazine. It provides an efficient method to reduce graphite oxide and could be used as a method to prepare novel composites.

Preparation and characterization of curdlan with unique single-helical conformation and its assembly with Congo Red.

Elucidating the structure-activity relationship of curdlan is hampered by a lack of characterization with unique specific conformations (i.e., single- or triple-helix). In this study, single-helical curdlan is generated in dilute NaOH solutions at 35-50 °C, and characterized with NMR, SAXS, and GPC. The conformational transition from coil to single-helix and the intramolecular hydrogen bond interaction are explored using NMR. It is found that the two aforementioned types of curdlan interact with Congo Red in very different ways. Single-helical curdlan can encapsulate Congo Red to form a stable, supramolecular dye assembly, which is demonstrated by the shortest distance between the H3 of curdlan and the phenyl groups of Congo Red, and also the same self-diffusion coefficients of Congo Red and curdlan. In contrast, random-coil curdlan interacts weakly with Congo Red and cannot enwrap it. This study offers insight into the specific structure-activity relationship of beta-(1,3)-glucans.

THz-enhanced dynamic nuclear polarized liquid spectrometer.

Dynamic nuclear polarization (DNP) technology can be utilized to dramatically enhance NMR signal. In this paper, we report on the development of a self-constructed 5 T DNP spectrometer for liquid samples and the 13C DNP enhancement achieved with this spectrometer. The DNP spectrometer is comprised of a wide-bore superconducting magnet, a home-made console, a dual resonance probe and a self-built 140 GHz microwave source for the spectrometer. Specifically, a microwave source of traveling wave tube (TWT) amplifier has been developed, which can provide a maximum power output of 4.4 W and a wide frequency tuning range of 1 GHz. The excellent performance of our built liquid-state DNP spectrometer is verified by the observation of more than 100-fold DNP enhancement of the 13C NMR signal for liquid 13CCl4 sample. Our result shows the superiority of DNP technology in the liquid-state high-field NMR spectrometer.

In Situ Characterization of Over-Lithiation of Organosulfide-Based Lithium Metal Anodes.

Over-lithiated organosulfides, such as sulfurized polyacrylonitrile (SPAN), are promising candidates of lithium metal anode (LMA) protection since they could form robust solid electrolyte interphases (SEIs), which is the key toward stable lithium metal batteries. So far, the mechanism of over-lithiation and evolution of the electrode surface is poorly understood. Herein, several in situ techniques were employed to study the over-lithiation process in SPAN, including in situ Raman spectroscopy to reveal the chemical transformation and in situ electrochemical atomic force microscopy (EC-AFM) to visualize interfacial evolution. The results undoubtedly prove the breaking of the C-S bond and formation of the C-Li bond during the over-lithiation process. The nucleophilic C-Li could further trigger the decomposition of the electrolyte to form an inorganic-organic hybrid SEI on the surface of SPAN, which allows uniform Li deposition and significantly improves the cycle stability of LMAs, as supported by the in situ EC-AFM characterization as well as a series of full cell tests. New insights into the over-lithiation mechanism of SPAN should facilitate the design of organosulfides to construct stable lithium metal anodes.

Dynamics and Glass Transition of Supercooled Water Confined in Amphiphilic Polymer Films.

The glass transition of supercooled water is not well understood yet. We have observed a clear glass transition of the supercooled water confined in channel of amphiphilic polymer films at 145 K. Using NMR, we probe two types of relaxations occurred in the glass former, e.g., a rapid local ß-process and a slow α-process (most likely). It is found that slow α-relaxation follows the Arrhenius relationship, indicating the glass former is a strong liquid. We also find a dynamic crossover from low-temperature Arrhenius α-process to high-temperature VFT process at 198-208 K, accompanying with simultaneous disappearing of local ß-relaxation.

New Li10GeP2S12 Structure Ordering and Li-Ion Dynamics Unveiled in Li4GeS4-Li3PS4 Superionic Conductors: A Solid-State Nuclear Magnetic Resonance Study.

The fast Li-ion pathways in crystals contribute to superionic conductivity-extraordinarily high ionic conductivity-of the Li10GeP2S12 (LGPS) structure. Composition tuning is expected to improve the conductivity. The phase behavior, microstructure, and ion dynamics of a series of solid solutions of xLi4GeS4-yLi3PS4 (4/1 ≥ x/y ≥ 1/2) were studied by multiple 7Li and 31P solid-state NMR methods. Li10GeP2S12 (Ge/P = x/y = 1/2) is the smallest x/y of the disordered LGPS structure. When the Ge/P ratio increases, the room-temperature Li ionic conductivity first increases to a maximum around x/y = 1/1.2 and then decreases. Meanwhile, a disordered LGPS structure transforms into an ordered LGPS' structure synchronously with conductivity reduction. The Li4GeS4-Li3PS4 phase diagram with the order-disorder structure transition was reconstructed accordingly. Both ordered LGPS' and disordered LGPS exhibit similar two-dimensional (2D) and one-dimensional (1D) Li diffusion paths. But the disordered LGPS structure is conducive to fast ionic conductivity, rooted in its fast 2D Li+ diffusion in the ab-plane rather than 1D diffusion along the c-axis. Two high-temperature relaxation processes are observed in the LGPS' structure, suggesting heterogeneous 2D jumps of rapid and slow rates, whereas only a single homogeneous 2D jump process was found in the LGPS structure. Our findings provide insight into understanding the relationship between structure order (or disorder) and ionic conductivity of superionic materials, offering guidelines for optimizing ionic conductivity for extensive solid electrolyte materials rather than LGPS materials.

Anomalous diffusion of chains in semicrystalline ethylene polymers.

The chain diffusion between crystalline and amorphous/interfacial regions in semicrystalline ethylene homo- and copolymers was investigated by means of solid-state NMR. It was found that the crystalline chain segment diffusion along the chain-folded path is anomalous and can be characterized by the scaling relation of mean-square displacement, approximately t(1/2).