Metal-Halogen Interactions Inducing Phase Separation for Self-Healing and Tough Ionogels with Tunable Thermoelectric Performance.

Ionic liquid-based thermoelectric gels become a compelling candidate for thermoelectric power generation and sensing due to their giant thermopower, good thermal stability, high flexibility, and low-cost production. However, the materials reported to date suffer from canonical trade-offs between self-healing ability, stretchability, strength, and ionic conductivity. Herein, a self-healing and tough ionogel (PEO/LiTFSI/EmimCl) with tunable thermoelectric properties by tailoring metal-halogen bonding interactions, is developed. Different affinities between polymer matrix and salts are exploited to induce phase separation, resulting in simultaneous enhancement of ionic conductivity and mechanical strength. Molecular dynamics (MD) simulations and spectroscopic analyses show that Cl- ions impair the lithium-ether oxygen coordination, leading to changes in chain conformation. The migration difference between cations and anions is thus widened and a transition from n-type to p-type thermoelectric ionogels is realized. Furthermore, the dynamic interactions of metal-ligand coordination and hydrogen bonding yield autonomously self-healing capability, large stretchability (2000%), and environment-friendly recyclability. Benefiting from these fascinating properties, the multifunctional PEO-based ionogels are applied in sensors, supercapacitors, and thermoelectric power generation modules. The strategy of tuning solvation dominance to address the trade-offs in thermoelectric ionogels and optimize their macroscopic properties offers new possibilities for the design of advanced ionogels.

Tuning the Interface Stability of Nickel-Rich NCM Cathode Against Aggressive Structural Collapse via the Synergistic Effect of Additives.

Nickel-rich layered oxides are envisaged as one of the most promising alternative cathode materials for lithium-ion batteries, considering their capabilities to achieve ultrahigh energy density at an affordable cost. Nonetheless, with increasing Ni content in the cathodes comes a severe extent of Ni4+ redox side reactions on the interface, leading to fast capacity decay and structural stability fading over extended cycles. Herein, dual additives of bis(vinylsulfonyl)methane (BVM) and lithium difluorophosphate (LiDFP) are adopted to synergistically generate the F-, P-, and S-rich passivation layer on the cathode, and the Ni4+ activity and dissolution at high voltage are restricted. The sulfur-rich layer formed by the polymerization of BVM, combined with the Li3PO4 and LiF phases derived from LiDFP, alleviates the problems of increased impedance, cracks, and an irreversible H2-H3 phase transition. Consequently, the Ni-rich LiNixM1-xO2 (x > 0.95) button half-cell cycled in LiDFP + BVM electrolyte exhibits a significant discharging capacity of 181.4 mAh g-1 at 1 C (1 C = 200 mA g-1) with retention of 83.7% after 100 cycles, surpassing the performance of the commercial electrolyte (160.7 mAh g-1) with retention of 53.3%. Remarkably, the NCM95||graphite pouch cell exhibits a remarkable capacity retention of 95.5% after 200 cycles. This work inspires the rational design of electrolyte additives for ultrahigh-energy batteries with nickel-rich layered oxide cathodes.

Liquid lens based holographic camera for real 3D scene hologram acquisition using end-to-end physical model-driven network.

With the development of artificial intelligence, neural network provides unique opportunities for holography, such as high fidelity and dynamic calculation. How to obtain real 3D scene and generate high fidelity hologram in real time is an urgent problem. Here, we propose a liquid lens based holographic camera for real 3D scene hologram acquisition using an end-to-end physical model-driven network (EEPMD-Net). As the core component of the liquid camera, the first 10 mm large aperture electrowetting-based liquid lens is proposed by using specially fabricated solution. The design of the liquid camera ensures that the multi-layers of the real 3D scene can be obtained quickly and with great imaging performance. The EEPMD-Net takes the information of real 3D scene as the input, and uses two new structures of encoder and decoder networks to realize low-noise phase generation. By comparing the intensity information between the reconstructed image after depth fusion and the target scene, the composite loss function is constructed for phase optimization, and the high-fidelity training of hologram with true depth of the 3D scene is realized for the first time. The holographic camera achieves the high-fidelity and fast generation of the hologram of the real 3D scene, and the reconstructed experiment proves that the holographic image has the advantage of low noise. The proposed holographic camera is unique and can be used in 3D display, measurement, encryption and other fields.

Molecular Coupling Strategy Achieving In Situ Synthesis of Agglomeration-Free Solid Composite Electrolytes.

Solid composite electrolytes (SCEs) synergize inorganic and polymer merits for viable commercial application. However, inferior filler-polymer interfacial stability ultimately leads to the agglomeration of inorganic particles and greatly impedes Li+ migration. Herein, triethoxyvinylsilane (VTEO) is employed to form a strong chemical interaction between poly(vinylene carbonate) (PVC) and montmorillonite (MMT) via in situ solidification, which eliminates the agglomeration and improves interfacial compatibility. Consequently, the obtained solid composite electrolytes (PVC-s-MMT) achieve increased Li+ conductivity (0.4 mS cm-1 at 25 °C), enhanced transference number (0.74), and increased oxidation potential (5.2 V). The Li/PVC-s-MMT/LiFePO4 cells exhibit outstanding cycling performance (>99.5% after 600 cycles) at 1C at room temperature. Moreover, density functional theory (DFT) calculations are applied to uncover the fast interfacial conducting channels of PVC-s-MMT. Our work provides a feasible in situ synthesis method to prepare agglomeration-free SCEs, which is highly compatible with existing battery production processes of liquid electrolytes.

Exceptional n-type thermoelectric ionogels enabled by metal coordination and ion-selective association.

Ionic liquid-based ionogels emerge as promising candidates for efficient ionic thermoelectric conversion due to their quasi-solid state, giant thermopower, high flexibility, and good stability. P-type ionogels have shown impressive performance; however, the development of n-type ionogels lags behind. Here, an n-type ionogel consisting of polyethylene oxide (PEO), lithium salt, and ionic liquid is developed. Strong coordination of lithium ion with ether oxygen and the anion-rich clusters generated by ion-preferential association promote rapid transport of the anions and boost Eastman entropy change, resulting in a huge negative ionic Seebeck coefficient (-15 millivolts per kelvin) and a high electrical conductivity (1.86 millisiemens per centimeter) at 50% relative humidity. Moreover, dynamic and reversible interactions among the ternary mixtures endow the ionogel with fast autonomous self-healing capability and green recyclability. All PEO-based ionic thermoelectric modules are fabricated, which exhibits outstanding thermal responses (-80 millivolts per kelvin for three p-n pairs), demonstrating great potential for low-grade energy harvesting and ultrasensitive thermal sensing.

Exploiting nonaqueous self-stratified electrolyte systems toward large-scale energy storage.

Biphasic self-stratified batteries (BSBs) provide a new direction in battery philosophy for large-scale energy storage, which successfully reduces the cost and simplifies the architecture of redox flow batteries. However, current aqueous BSBs have intrinsic limits on the selection range of electrode materials and energy density due to the narrow electrochemical window of water. Thus, herein, we develop nonaqueous BSBs based on Li-S chemistry, which deliver an almost quadruple increase in energy density of 88.5 Wh L-1 as compared with the existing aqueous BSBs systems. In situ spectral characterization and molecular dynamics simulations jointly elucidate that while ensuring the mass transfer of Li+, the positive redox species are strictly confined to the bottom-phase electrolyte. This proof-of-concept of Li-S BSBs pushes the energy densities of BSBs and provides an idea to realize massive-scale energy storage with large capacitance.

Achieving Rapid Ultralow-Temperature Ion Transfer via Constructing Lithium-Anion Nanometric Aggregates to Eliminate Li+-Dipole Interactions.

Sluggish desolvation in extremely cold environments caused by strong Li+-dipole interactions is a key inducement for the capacity decline of a battery. Although the Li+-dipole interaction is reduced by increasing the electrolyte concentration, its high viscosity inevitably limits ion transfer at low temperatures. Herein, Li+-dipole interactions were eliminated to accelerate the migration rate of ions in electrolytes and at the electrode interface via designing Li+-anion nanometric aggregates (LA-nAGGs) in low-concentration electrolytes. Li+ coordinated by TFSI- and FSI- anions instead of a donor solvent promotes the formation of an inorganic-rich interfacial layer and facilitates Li+ transfer. Consequently, the LA-nAGG-type electrolyte demonstrated a high ionic conductivity (0.6 mS cm-1) at -70 °C and a low activation energy of charge transfer (38.24 kJ mol-1), enabling Li||NiFe-Prussian blue derivative cells to deliver ∼83.1% of their room-temperature capacity at -60 °C. This work provides an advanced strategy for the development of low-temperature electrolytes.

Method of color holographic display with speckle noise suppression.

In this paper, a method of color holographic display with speckle noise suppression is proposed. Firstly, the intensity information of the object is extracted according to the red, green and blue (RGB) channels. The band-limited phase is calculated and used as the initial phase for each color channel. Secondly, the double-step Fresnel diffraction algorithm is used to calculate the computer-generated holograms (CGHs), and a filter plane that dynamically adjusts the position of the filter in the optical path is designed. Then, a divergent spherical phase factor is added to the CGHs. Finally, the time average method is used to further reduce the speckle noise. When the CGHs of the RGB channels are loaded on the digital micromirror device and illuminated by the RGB lights emitting in a temporal sequence, the color reconstructed images with speckle noise suppression can be displayed. The validity of the proposed method is verified.

Holographic near-eye display system with large viewing area based on liquid crystal axicon.

In this paper, a liquid crystal axicon based holographic near-eye display system with large viewing area is proposed. The viewing area of the system is extended by implementing the liquid crystal axicon. The error diffusion algorithm is used to calculate the computer-generated hologram (CGH). When incident on the liquid crystal axicon placed at the back focal plane of Fourier lens, the reconstruction light modulated by the CGH is deflected into two directions resulting in a viewing area extension. Meanwhile, to illustrate the potential of the proposed system, two-dimensional viewing area extension is demonstrated. It combines the frequency spectrum shift with the proposed system and achieves a double expansion of the horizontal viewing area and three-times expansion of the vertical viewing area. Feasibility of the proposed system is verified by optical experiments. The proposed system has potential applications in holographic augmented reality (AR) display.

The influence and acting pattern of China's national carbon emission trading scheme on regional ecologicalization efficiency of industry.

To achieve the goal of energy conservation and emission reduction, China has launched its national carbon-emission trading scheme (ETS). Therefore, it is of great significance to evaluate the implementation of ETS from the perspective of regional ecologicalization efficiency of industry. Based on the panel data of 30 provinces and cities from 2007 to 2019, this study takes the SBM-DEA model to measure the regional ecologicalization efficiency of industry, uses the Difference-in-Difference (DID) model to evaluate the influence of ETS on the regional ecologicalization efficiency of industry, and verifies the outcome by propensity score matching method and counterfactual test. The mediating effect model is used to test the acting pattern of ETS on the regional ecologicalization efficiency of industry. The results show that: (1) ETS can significantly improve the ecologicalization efficiency of industry and shows regional heterogeneity. (2) ETS promotes regional energy conservation, emission reduction, and economic development because of the upgrading of structural optimization, agglomeration of resource synergy, and optimization of ecology. This study offers penetrating insights into the positive operation of the carbon market and provides some useful hints for the development of China's regional economy.

Tunable liquid crystal grating based holographic 3D display system with wide viewing angle and large size.

As one of the most ideal display approaches, holographic 3-dimensional (3D) display has always been a research hotspot since the holographic images reproduced in such system are very similar to what humans see the actual environment. However, current holographic 3D displays suffer from critical bottlenecks of narrow viewing angle and small size. Here, we propose a tunable liquid crystal grating-based holographic 3D display system with wide viewing angle and large size. Our tunable liquid crystal grating, providing an adjustable period and the secondary diffraction of the reconstructed image, enables to simultaneously implement two different hologram generation methods in achieving wide viewing angle and enlarged size, respectively. By using the secondary diffraction mechanism of the tunable liquid crystal grating, the proposed system breaks through the limitations of narrow viewing angle and small size of holographic 3D display. The proposed system shows a viewing angle of 57.4°, which is nearly 7 times of the conventional case with a single spatial light modulator, and the size of the reconstructed image is enlarged by about 4.2. The proposed system will have wide applications in medical diagnosis, advertising, education and entertainment and other fields.

Self-Assembled Nanospheres with Enhanced Interfacial Lubrication for the Treatment of Osteoarthritis.

Osteoarthritis is associated with an increase in mechanical friction of the joint, which causes irreversible damage to articular cartilage. Consequently, it is crucial to restore joint lubrication for effectively treating osteoarthritis. In the present study, hyaluronic acid (HA)-based zwitterionic nanospheres with phosphocholine groups on the surface were synthesized, which achieved excellent lubrication behavior due to the hydration lubrication mechanism. Specifically, HA was initially thiolated and modified with hexadecylamine based on an amidation reaction, then it was grafted with 2-methacryloyloxyethyl phosphocholine (MPC) by the thiol-ene click reaction, and finally self-assembled into nanospheres (HA-MPC) by hydrophobic interaction and cross-linking of the thiol group. The lubrication test demonstrated that the HA-MPC nanospheres improved lubrication under shear force, with a 40% reduction in the friction coefficient compared with HA. The in vitro experiment indicated that the HA-MPC nanospheres had excellent biocompatibility, and they upregulated the cartilage anabolic gene and downregulated cartilage catabolic proteases as well as the pain-related gene. The in vivo test showed that the injection of HA-MPC nanospheres to the joint cavity could inhibit the development of osteoarthritis, which was examined based on histological staining and also morphological evaluation. In conclusion, the new self-assembled zwitterionic HA-MPC nanospheres may be intra-articularly injected for the effective treatment of osteoarthritis by restoring joint lubrication.

Tailoring Intermolecular Interactions Towards High-Performance Thermoelectric Ionogels at Low Humidity.

Development of ionic thermoelectric (iTE) materials is of immense interest for efficient heat-to-electricity conversion due to their giant ionic Seebeck coefficient (Si ), but challenges remain in terms of relatively small Si at low humidity, poor stretchability, and ambiguous interaction mechanism in ionogels. Herein, a novel ionogel is reported consisting of polyethylene oxide (PEO), polyethylene oxide-polypropylene oxide-polyethylene oxide (P123), and 1-ethyl-3-methylimidazolium acetate (Emim:OAC). By delicately designing the interactions between ions and polymers, the migration of anions is restricted due to their strong binding with the hydroxyl groups of polymers, while the transport of cations is facilitated through segmental motions due to the increased amorphous regions, thereby leading to enlarged diffusion difference between the cations and anions. Moreover, the plasticizing effect of P123 and Emim:OAC can increase the elongation at break. As a consequence, the ionogel exhibits excellent properties including high Si (18 mV K-1 at relative humidity of 60%), good ionic conductivity (1.1 mS cm-1 ), superior stretchability (787%), and high stability (over 80% retention after 600 h). These findings show a promising strategy to obtain multifunctional iTE materials by engineering the intermolecular interactions and demonstrate the great potential of ionogels for harvesting low-grade heat in human-comfortable humidity environments.

Surpassing the Redox Potential Limit of Organic Cathode Materials via Extended p-π Conjugation of Dioxin.

The key to enabling high energy density of organic energy-storage systems is the development of high-voltage organic cathodes; however, the redox voltage (<4.0 V vs Li/Li+) of state-of-the-art organic electrode materials (OEMs) remains unsatisfactory. Herein, we propose a novel dibromotetraoxapentacene (DBTOP) redox center to surpass the redox potential limit of OEMs, achieving ultrahigh discharge plateaus of approximately 4.4 V (vs Li+/Li). As theoretically analyzed, electron delocalization between dioxin active centers and benzene rings as well as electron-withdrawing bromine atoms endows the molecule with a low occupied molecular orbital level by diluting the electron density of dioxin in the whole p-π conjugated skeleton, and the strong π-π interactions among the DBTOP molecules provide a faster electrochemical kinetic pathway. This tetraoxapentacene redox center makes the working voltage of OEMS closer to the high-voltage inorganic electrodes, and its chemical and structural tunability may stimulate the further development of high-voltage organic cathodes.

Effect of Acupoint Catgut Embedding for Middle-Aged Obesity: A Multicentre, Randomised, Sham-Controlled Trial.

Objectives: This study aimed to examine the efficacy and safety of acupoint catgut embedding (ACE) for obesity over a 16-week treatment period using sham stimulation as the control. Methods: A multicenter, randomised, parallel, sham-controlled trial was conducted from February 10, 2017, to May 15, 2018. Men with waistlines ≥85 cm and women with ≥80 cm at three sites were randomised to receive eight sessions (over 16 weeks) of ACE (n = 108) or sham ACE (n = 108) with skin penetration at sham acupoints. The catgut was embedded once every two weeks using two alternating sets of acupoints. The follow-up lasted for an additional 24 weeks. The primary outcome was the percentage waistline reduction from baseline to week 16. Results: We included 216 individuals in the intention-to-treat analysis. At 16 weeks, the rate of waistline reduction was 8.80% (95% confidence interval (CI), 7.93% to 9.66%) in the ACE group and 4.09% (95% CI, 3.18% to 5.00%) in the sham control group, with a between-group difference of 4.71% (95% CI, 3.47% to 5.95%; P < 0.0001). This difference persisted throughout the entire follow-up period (between-group difference after 24-week additional weeks, 4.94% (95% CI, 3.58% to 6.30%); P < 0.001). The subgroup analyses of waistline by sex (male/female) revealed treatment effects of 1.93 (95% CI, -0.37 to 4.23, P = 0.1) in the male group and 3.19 (95% CI, 1.99 to 4.39, P < 0.001) in the female group. The adverse event analysis suggested that ACE and laboratory tests confirmed the safety of ACE. Discussion. ACE for 16 weeks could decrease the waistline and weight and was safe for the treatment of obesity. Further research is needed to evaluate the long-term efficacy and sex differences. This trial is registered with NCT02936973.

Accelerating Ion Dynamics Under Cryogenic Conditions by the Amorphization of Crystalline Cathodes.

The normal operation of lithium-ion batteries (LIBs) at ultralow temperature (<-40 °C) is significant for cold-climate applications; however, their operation is plagued by the low capacity of the conventional intercalation cathodes due to their sluggish kinetics and the slow solid diffusion of Li+ in their frameworks. Here, it is demonstrated that amorphization is an effective strategy to promote the low-temperature dynamics of cathodes by relieving the blocking effect of a dense lattice structure on ion transport under cryogenic conditions. As a result, due to the decreased charge transport impedance and enhanced Li+ diffusion rate, the obtained covalent amorphous polymer (CAP) with an abundance of pyrazine and carbonyl active sites displays a remarkably outstanding specific capacity of 141 mAh g-1 at -80 °C, which is superior to its structural analog, a covalent crystalline polymer (43.8 mAh g-1 ). Furthermore, 84.7% of the initial capacity of the CAP can be retained after 500 cycles of charge and discharge at -60 °C. Molecular dynamic simulations show that the channel-rich amorphous structure is highly conducive for lithium ions to diffuse quickly in the interstitial space of organic solids. This work provides an effective strategy regarding the amorphization of crystalline cathodes to develop low-temperature (Low-T) batteries.

A ZIF-8 Host for Dendrite-Free Zinc Anodes and N,O Dual-doped Carbon Cathodes for High-Performance Zinc-Ion Hybrid Capacitors.

Zn is a promising anode for aqueous energy storage owing to it intrinsic superior properties such as large capacity, abundant reserves, low potential and safety. But, the growth of dendrites during charge and discharge leads to a decrease in reversibility. In addition, further development of zinc-ion hybrid capacitors (ZICs) is seriously challenging because of the lack of an exceptional cathode. Herein, we use ZIF-8 annealed at 500 °C (annealed ZIF-8) as a host material for stable and dendrite-free Zn anodes. Utilization of annealed ZIF-8 results in dendrite-free Zn deposition and stripping as a result of its porous construction, which contains trace Zn. Furthermore, we firstly proposed innovative N,O dual-doped carbon which was designed by the derived ZIF-8 (ZIF-8 derived C) as cathode for high-energy and power-density ZICs. The new ZIC assembled by Zn@annealed ZIF-8 anode and ZIF-8 derived C cathode provides a capacity of 135.5 mAh g-1 and an energy density of 108.4 Wh kg-1 with a power density of 800 W kg-1 at 1.0 A g-1 . In addition, it shows outstanding cycling stability of 91% capacity retention after 6000 cycles at 5.0 A g-1 . Moreover, the solid-state ZICs can drive LEDs and smart watches. This ZIC holds promise for the practical application of supercapacitors.

Self-adhesive lubricated coating for enhanced bacterial resistance.

Limited surface lubrication and bacterial biofilm formation pose great challenges to biomedical implants. Although hydrophilic lubricated coatings and bacterial resistance coatings have been reported, the harsh and tedious synthesis greatly compromises their application, and more importantly, the bacterial resistance property has seldom been investigated in combination with the lubrication property. In this study, bioinspired by the performances of mussel and articular cartilage, we successfully synthesized self-adhesive lubricated coating and simultaneously achieved optimal lubrication and bacterial resistance properties. Additionally, we reported the mechanism of bacterial resistance on the nanoscale by studying the adhesion interactions between biomimetic coating and hydrophilic/hydrophobic tip or living bacteria via atomic force microscopy. In summary, the self-adhesive lubricated coating can effectively enhance lubrication and bacterial resistance performances based on hydration lubrication and hydration repulsion, and represent a universal and facial strategy for surface functionalization of biomedical implants.

Effect of Membrane Properties on the Carbonation of Anion Exchange Membrane Fuel Cells.

Anion exchange membrane fuel cells (AEMFC) are potentially very low-cost replacements for proton exchange membrane fuel cells. However, AEMFCs suffer from one very serious drawback: significant performance loss when CO2 is present in the reacting oxidant gas (e.g., air) due to carbonation. Although the chemical mechanisms for how carbonation leads to voltage loss in operating AEMFCs are known, the way those mechanisms are affected by the properties of the anion exchange membrane (AEM) has not been elucidated. Therefore, this work studies AEMFC carbonation using numerous high-functioning AEMs from the literature and it was found that the ionic conductivity of the AEM plays the most critical role in the CO2-related voltage loss from carbonation, with the degree of AEM crystallinity playing a minor role. In short, higher conductivity-resulting either from a reduction in the membrane thickness or a change in the polymer chemistry-results in faster CO2 migration and emission from the anode side. Although this does lead to a lower overall degree of carbonation in the polymer, it also increases CO2-related voltage loss. Additionally, an operando neutron imaging cell is used to show that as AEMFCs become increasingly carbonated their water content is reduced, which further drives down cell performance.

Adsorption removal of Ni(II) and phenol from aqueous solution by modified attapulgite and its composite hydrogel.

Attapulgite (ATP) and its organically modified products have been investigated for potential applications in environmental remediation. In this work, a variety of modifiers with different functional groups, including saturated sodium chloride solution (NaCl), cetyltrimethyl ammonium bromide (CTAB) and humic acid (HA), were used to treat attapulgite clay firstly, and then with the modified ATP as adsorbent and acrylamide (AAm) as monomer, polyacrylamide/modified attapulgite (PAAm/modified ATP) composite hydrogel which could adsorb heavy metal ions Ni(II) and organic pollutants phenol were synthesized. The structure of the raw ATP and modified ATP was specified with Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and Transmission electron microscope (TEM). The experiments indicated that the modified ATP and composite hydrogel possessed good adsorption properties for Ni(II) ions and phenol. The adsorption capacity of PAAm/HA-ATP hydrogel for Ni(II) was as high as 64.3 mg/g, which was 194.9% of pure hydrogel. The adsorption isotherm of HA-modified ATP (HA-ATP) and adsorption kinetics of PAAm/HA-ATP composite hydrogel was particularly concerned. The adsorption isotherm equation fitted well on the Langmuir model and RL values ranged from 0.04 to 0.12 with different temperatures, indicated that the HA-ATP was a suitable adsorbent for adsorption of Ni(II) ions from wastewater. The obtained kinetics data for Ni(II) ions adsorption onto the PAAm/HA-ATP were described well by the pseudo-second-order model (R2 > 0.99). As for the adsorption of phenol, double-modification proved to be the most effective method, and its optimal adsorption capacity was obtained on PAAm/CTAB-HA-ATP hydrogel.