Unraveling the underlying mechanism of good electrochemical performance of hard carbon in PC/EC-Based electrolyte.

Although hard carbon in propylene carbonate / ethylene carbonate (PC/EC)-based electrolytes possesses favorable electrochemical characteristics in rechargeable sodium-ion batteries, the underlying mechanism is still vague. Numerous hypotheses have been proposed to solve the puzzle, but none of them have satisfactorily unraveled the reason at the molecular-level. In this study, we firstly attempted to address this mystery through a profound insight into the disparity of the ion solvation/desolvation behavior in electrolyte. Combining the results of density functional theory (DFT) calculations and experiments, the work explains that compared to the sole PC-based electrolyte, Na+-EC4 molecules in the PC/EC-based electrolyte preferentially undergo reduction and contribute to the emergence of a more stable protective film on the surface of hard carbon, leading to the preferable durability and rate capability of the cell. Nevertheless, applying the ion solvation/desolvation model, it also reveals that Na+-(solvent)n molecules in the PC/EC-based electrolyte can achieve faster Na+ desolvation processes than in the PC-based electrolyte alone, contributing to the enhancement of charge transfer kinetics. This research holds great importance in uncovering the possible mechanism of the remarkable electrochemical- properties of hard carbon in PC/EC-based electrolytes, and advancing its practical utilization in future sodium-ion batteries.

A strontium ferrite modified separator for adsorption and catalytic conversion of polysulfides for excellent lithium-sulfur batteries.

Lithium-sulfur batteries (LSBs) have emerged as one of the ideal contenders for the upcoming generation of high energy storage devices due to their superb energy density. Nonetheless, the shuttle effect generated by intermediate lithium polysulfides (LiPSs) during cell cycling brings about capacity degradation and poor cycling stability of LSBs. Here, a versatile SrFe12O19 (FSO) and acetylene black (AB) modified PP separator is first presented to inhibit the shuttle effect. Thanks to the strong chemical interaction of Fe and Sr with polysulphides in FSO, it can trap LiPSs and provide catalytic sites for their conversion. Therefore, the cell using the FSO/AB@PP separator has a high initial discharge specific capacity (930 mA h g-1) at 2 C and lasts for 1000 cycles with a remarkably low fading rate (0.036% per cycle), while those using PE and AB@PP separators have inferior initial specific capacities (255 mA h g-1 and 652 mA h g-1, respectively) and fail within 600 cycles. This work proposes a novel approach for addressing the shuttle of LiPSs from a bimetallic oxide modified separator.

Mechanistic insights into the formation of surface oxygen vacancies with controllable concentration and long-term stability in small-molecule bonded bismuth-based semiconductor hybrid photocatalyst.

Constructing oxygen vacancies (OVs) with desired concentration and stability on the surfaces of semiconductors has been demonstrated to be a powerful tactic to enhance their photocatalytic performances. Nevertheless, forming OVs usually requires rigorous conditions, and OVs harshly suffer from deactivation during photoreaction. Herein, a facile strategy is developed to introduce surface OVs with tunable concentrations and long-term stability in bismuth-based semiconductors (BBS) through organic small-molecule surface-bonding. Taking I-doped BiOCl (I-BiOCl) as a model photocatalyst and catechol and its derivatives as ligands, a series of organic/I-BiOCl bonded hybrid photocatalysts are successfully synthesized. Compared with I-BiOCl, hybrid photocatalysts exhibited substantially enhanced catalytic activity toward multiple contaminants removal. Experimental characterizations and DFT calculations reveal a strong interfacial interaction between organic ligands and BBS through the formation of BiOC bonds, which lengthen Bi-O bonds within [Bi2O2]2+ structural units and reduce the formation energy of OVs, facilitating the escape of lattice O atoms and thus producing abundant surface OVs. More importantly, the concentration of OVs can be easily regulated by controlling the number of organic ligands, and the OVs exhibit high stability during photoreaction, attributing to the existence of high-valence-state Bi(3+x)+ that is near the OVs, which would not be re-oxidized by oxidative species like the low-valence-state Bi(3-x)+, that is, they would not be reset to original Bi3+. As a verification of its universality, the surface bonded strategy has been successfully extended to other BBS.

1,2,3,4-Tetrakis(2-cyanoethoxy)butane (TCEB)-Assisted Construction of Self-Repair Electrode Interface Films to Improve the Performance of 4.5 V Pouch LiCoO2/Artificial Graphite Full Cells Operating at 45 °C.

1,2,3,4-Tetrakis(2-cyanoethoxy)butane (TCEB) is first evaluated as a functional electrolyte additive to increase the charge cutoff voltage and energy density of pouch LiCO2 (LCO)/artificial graphite (AG) lithium-ion batteries (LIBs) at a high temperature of 45 °C. The charge (0.7 C) and discharge (1 C) tests show that TCEB effectively improves the cycle stability of cells under a high charge cutoff voltage of 4.5 V. At 25 °C, the capacity retention of the cells with TCEB increases from 0.0% to 72.1% after 1200 cycles. At 45 °C, the capacity retention of the cells without TCEB after 50 cycles is close to 0.0%, while the capacity retention of the cells with TCEB is still 81.6%, even after 350 cycles. The spectroscopic characterization results demonstrate that the TCEB electrolyte additive participates in the construction of a self-repair electrode/electrolyte interface film. Subsequently, low impedance and strong protective layers are formed on the two electrode surfaces. The quantitative analysis results and a theoretical calculation also show that TCEB effectively inhibits the dissolution of Co3+ and maintains the structural integrity of electrode materials. These results indicate that TCEB endows LIBs with excellent cycle stability and is a promising electrolyte additive for the high-voltage and high-temperature conditions of LCO-based LIBs.

Efficient and effective removal of emerging contaminants through the parallel coupling of rapid adsorption and photocatalytic degradation: A case study of fluoroquinolones.

The development of efficient, effective, and large-scale treatment methods to address high-risk emerging contaminants (ECs) is a growing challenge in environmental remediation. Herein, a novel parallel coupling strategy of adsorption separation and photodegradation regeneration (parallel ASPR) is proposed; subsequently, an adsorptive photocatalyst (Zn-doped BiOI) is designed to demonstrate how to effectively eliminate fluoroquinolones (FQs) from water with the proposed ASPR scheme. Compared with pure BiOI, the addition of Zn2+ during synthesis has a significant influence on the morphology and structure of the products, resulting in Zn-doped BiOI samples with up to 5 times the specific surface area, 32 times the adsorption capacity, and 20 times the photocurrent intensity. The optimized Zn-doped BiOI sample has an excellent adsorption efficiency for FQs with a removal rate that exceeds 95% after 5 min of adsorption for all 6 tested FQ antibiotics. Then the adsorbed contaminants can be effectively degraded during the later visible-light irradiation process, and the adsorbent can be regenerated synchronously, showing excellent ASPR cycling performances. The mechanisms of rapid adsorption and photocatalysis were explored via material characterizations, adsorption models, density functional theory calculations, and photogenerated species analyses. The results reveal that the enhanced adsorption of Zn-doped BiOI for FQs is due to its high specific surface area, coordination-based chemical adsorption, and surface electrostatic attraction, while its superior visible-light photodegradation performance is mainly ascribed to its strong redox ability, abundant surface oxygen vacancies, and enhanced photogenerated carrier separation efficiency.

A Heat-Resistant Poly(oxyphenylene benzimidazole)/Ethyl Cellulose Blended Polymer Membrane for Highly Safe Lithium-Ion Batteries.

A blended membrane based on poly(oxyphenylene benzimidazole) (PBI) and ethyl cellulose (EC) exhibits heat resistance and good electrochemical performance. The prepared blended polymer gel membranes show no visible dimensional change after being held at 350 °C for 30 min, whereas the polyethylene (PE) separator almost completely melts. In addition to excellent thermal stability, the self-supporting blended membranes also exhibit a uniform thermal distribution during the heating process from 60 to 200 °C. Additionally, the ionic conductivities of the PBI/EC blended membranes with different ratios are 1.24 mS cm-1 (1:1), 2.58 mS cm-1 (1:2), and 1.68 mS cm-1 (1:3), which are much higher than those of the PE separator (0.39 mS cm-1). Compared to that of the PE separator (113 mAh g-1), the cell with a separator of PBI/EC = 1:2 retained a discharge capacity of 131 mAh g-1 after 150 cycles at 0.5C. Meanwhile, the rate performance of the cell was also better than that of the PE separator, especially at high currents (5C). All of the results indicate that this blended polymer gel membrane with good thermal stability is expected to be applied to high-performance lithium-ion batteries.

Microwave synthesis of iodine-doped bismuth oxychloride microspheres for the visible light photocatalytic removal of toxic hydroxyl-contained intermediates of parabens: catalyst synthesis, characterization, and mechanism insight.

The iodine-doped bismuth oxychloride (I-doped BiOCl) microspheres are synthesized as the visible light photocatalysts for the photocatalytic removal of three toxic hydroxyl-contained intermediates of parabens. With the aid of the unique heating mode of microwave method, the I-doped BiOCl photocatalysts with tunable iodine contents and dispersed energy bands, instead of a mixture of BiOI and BiOCl or solid solution, are synthesized under the controllable conditions. Due to the stretched architectures, high specific surface area, and effective separation of photogenerated carriers, they exhibit high activity to the photocatalytic degradation of methyl 2,4-dihydroxybenzoate (MDB), methyl 3,4-dihydroxybenzoate (MDHB), and ethyl 2,4-dihydroxybenzoate (EDB). As a typical result, it is indicated that though MDB as the most difficult intermediate of parabens to be degraded, a 91.2% removal ratio can still be achieved over the I-doped BiOCl with an energy band of 2.79 eV within 60 min. In addition, it is also confirmed that these photocatalysts remain stable throughout the photocatalytic reaction and can be reused, and more importantly, the photogenerated h+ and •O2- are the key reactive species, while •OH plays a negligible role in the photocatalytic reaction. Resorcinol was identified as the main photodegraded intermediate. These results demonstrate that this photocatalytic system not only exhibit a high efficiency but also avoid the consequent secondary pollutions due to the no formation of complex hydroxyl derivatives.

Three-Dimensional Rigidity-Reinforced SiOx Anodes with Stabilized Performance Using an Aqueous Multicomponent Binder Technology.

Three-dimensional (3D) rigidity-reinforced SiOx anodes are prepared using the aqueous multicomponent binders to stabilize the performances of lithium-ion batteries. Considering an elastic skeleton, adhesiveness, electrolyte absorption, etc., four kinds of binders [polyacrylamide (PAM), poly(tetrafluoroethylene) (PTFE), carboxymethyl cellulose, and styrene butadiene rubber (SBR)] are selected to prepare aqueous multicomponent binders. The SiOx anodes with the binder PAM/SBR/PTFE (PSP) exhibit a 3D rigidity-reinforced structure, larger adhesive force, and moderate electrolyte adsorption capacity compared to other anodes with single and multicomponent binders. Specifically, the electrochemical performances of the SiOx anodes with the binder PSP663 are stabilized, and a retention capacity of 770 mAh g-1 at 500 mA g-1 after 300 cycles and a rate capacity of 993 mAh g-1 at 1200 mA g-1 are obtained. The enhanced performances are attributed to the good chemical stability of PTFE to protect SiOx particles from the electrolyte corrosion and to ensure electrode integrity. SBR acts as the binder backbone due to the strong adhesion force and specific three-dimensional structure. The rigidity of PAM limits the excessive expansion of SiOx particles well and shortens the ion migration. These results indicate that the 3D rigidity-reinforced SiOx anode with the aqueous binder PSP663 has promising prospects for practical application, and the results also provide a reference for solving the expansion problem of the silicon materials.

2,3,4,5,6-Pentafluorophenyl Methanesulfonate as a Versatile Electrolyte Additive Matches LiNi0.5Co0.2Mn0.3O2/Graphite Batteries Working in a Wide-Temperature Range.

An electrolyte using 2,3,4,5,6-pentafluorophenyl methanesulfonate (PFPMS) as a versatile additive is investigated through calculating the molecular orbital energies of additives and solvents and designing the electrolyte composition, and the comparative performances of LiNi0.5Co0.2Mn0.3O2/graphite cells operating in a wide-temperature range are improved. It is revealed that PFPMS can form interfacial films on both the cathode and anode surfaces, resulting in a decrease of the cell impedance and the side reactions between the active materials and electrolyte. Compared to the cells without additive of 74.9% and those with vinylene carbonate (VC) of 76.7%, the cycling retention of the cell with 1.0 wt % PFPMS reaches 91.7% after 400 cycles at room temperature. In particular, for the high-temperature storage at 60 °C for 7 d, the cell containing 1.0 wt % PFPMS exhibits optimal capacity retention of 86.3% and capacity recovery of 90.6%; for the low-temperature discharge capacity retention at -20 °C, the cell with 1.0 wt % PFPMS maintains at 66.3% at 0.5 C, while for the cells without additive and containing 1.0 wt % VC, their retention values are 55.0 and 62.1%, respectively. The excellent cycling, wide-temperature practicability, and rate capability of the cells with PFPMS demonstrate that the electrolyte with PFPMS additive is promising for applications in LiNi0.5Co0.2Mn0.3O2/graphite batteries.

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials.

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn-Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H2SO4 (2 mol L(-1)) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ⩾99.8% is recovered in an electrolytic cell with a cathode efficiency of ⩾85% under the conditions of 37-40°C and 300 A m(-2). The most of MnO2 and a small quantity of electrolytic MnO2 are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi0.5Mn1.5O4 material of lithium-ion battery. The as-synthesized LiNi0.5Mn1.5O4 discharges 118.3 mAh g(-1) capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO2. This process can recover the substances in the spent Zn-Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.

One-pot solvothermal synthesis of three-dimensional (3D) BiOI/BiOCl composites with enhanced visible-light photocatalytic activities for the degradation of bisphenol-A.

Three-dimensional (3D) BiOI/BiOCl composite microspheres with enhanced visible-light photodegradation activity of bisphenol-A (BPA) are synthesized by a simple, one-pot, template-free, solvothermal method using BiI(3) and BiCl(3) as precursors. These 3D hierarchical microspheres with heterojunction structures are composed of 2D nanosheets and have composition-dependent absorption properties in the ultraviolet and visible light regions. The photocatalytic oxidation of BPA over BiOI/BiOCl composites followed pseudo first-order kinetics according to the Langmuir-Hinshelwood model. The highest photodegradation efficiency of BPA, i.e., nearly 100%, was observed with the BiOI/BiOCl composite (containing 90% BiOI) using a catalyst dosage of 1 g L(-1) in the BPA solution (C(0)=20 mg L(-1), pH=7.0) under visible light irradiation for 60 min. Under these conditions, the reaction rate constant was more than 4 and 20 times greater than that of pure BiOI and the commercially available Degussa P25, respectively. The superior photocatalytic activity of this composite catalyst is attributed to the suitable band gap energies and the low recombination rate of the photogenerated electron-hole pairs due to the presence of BiOI/BiOCl heterostructures. Only one intermediate at m/z 151 was observed in the photodegradation process of BPA by liquid chromatography combined with mass spectrometry (LC-MS) analysis, and a simple and hole-predominated photodegradation pathway of BPA was subsequently proposed. Furthermore, this photocatalyst exhibited a high mineralization ratio, high stability and easy separation for recycling use, suggesting that it is a promising photocatalyst for the removal of BPA pollutants.

Efficient adsorption and visible-light photocatalytic degradation of tetracycline hydrochloride using mesoporous BiOI microspheres.

A novel microsphere-like BiOI hierarchical material was successfully synthesized by a one-step solution method at room temperature using polyvinylpyrrolidone (PVP) as structure directing reagent, its morphology, structure, surface area, photoabsorption were characterized, and the removal of tetracycline hydrochloride (TC) was evaluated under dark adsorption and visible light irradiation. It was shown that the BiOI microspheres formed in the precursor solution with PVP exhibit a mesoporous surface layer, 28.1m(2)g(-1) surface area, 1.91 eV band gap energy (E(g) value), and twofold removal ability to tetracycline hydrochloride (TC), i.e. adsorptive separation and visible light photocatalytic degradation. The adsorption process of TC on BiOI microspheres can be described by pseudo-second-order kinetics model and both Freundlich and Langmuir equations well described the adsorption isotherm but the former is better. More importantly, the BiOI microspheres exhibit an excellent photocatalytic degradation and mineralization capability to TC under visible light irradiation, which comes from its electronic band structure, high surface area and high surface-to-volume ratio. In addition, the BiOI microspheres are stable during the reaction and can be used repeatedly, showing promising prospect for the treatment of TCs in future industrial application.

Adsorptive separation and photocatalytic degradation of methylene blue dye on titanate nanotube powders prepared by hydrothermal process using metal Ti particles as a precursor.

Titanate nanotube powders (TNTPs) with the twofold removal ability, i.e. adsorptive separation and photocatalytic degradation, are synthesized under hydrothermal conditions using metal Ti particles as a precursor in the concentrated alkaline solution, and their morphology, structure, adsorptive and photocatalytic properties are investigated. Under hydrothermal conditions, the titanate nanotubes (TNTs) with pore diameter of 3-4nm are produced on the surface of metal Ti particles, and stacked together to form three-dimensional (3D) network with porous structure. The TNTPs synthesized in the autoclave at 130°C for 24h exhibits a maximum adsorption capability of about 197mg g(-1) in the neutral methylene blue (MB) solution (40mg L(-1)) within 90min, the adsorption process can be described by pseudo second-order kinetics model. Especially, in comparison with the adsorptive and the photocatalytic processes are performed in turn, about 50min can be saved through synchronously utilizing the double removal ability of TNTPs when the removal ratio of MB approaches 95% in MB solution (40mg L(-1)) at a solid-liquid (S/L) ratio of 1:8 under ultraviolet (UV) light irradiation. These 3D TNTPs with the twofold removal properties and easier separation ability for recycling use show promising prospect for the treatment of dye pollutants from wastewaters in future industrial application.