Layered Na2Ti3O7 as an Ultrastable Intercalation-Type Anode for Non-Aqueous Calcium-Ion Batteries.

Calcium ion batteries (CIBs) are a promising energy storage device due to the low redox potential of the Ca metal and the abundant reserves of the Ca element. However, the large radius and divalent nature of Ca2+ lead to its slow ion diffusion kinetics and the lack of suitable electrode materials for Ca storage. Here, a layered structure of Na2Ti3O7 (NTO) is presented as an anode material for nonaqueous CIBs. This NTO anode demonstrates a high discharge capacity of 165 mA h g-1 at 100 mA g-1 and a remarkable capacity retention rate of 80%, even after 2000 cycles at 500 mA g-1, surpassing the performance of all reported intercalation-type anode materials for CIBs. The NTO transfers to layered CaVIINaIXTi3O7 (CNTO) with intercalation of Ca2+ and extraction of Na+ during the first discharge process. Then, the CNTO undergoes the reversible insertion/extraction of Ca2+ during subsequent cycling. Additionally, density functional theory calculations reveal that NTO possesses a rapid two-dimensional diffusion pathway for Ca2+. Moreover, the full CIBs based on NTO as the anode further underscore its potential for CIBs. This work presents promising anode materials for CIBs, offering opportunities to promote the development of high-performance CIBs.

Deeper Insights into the Morphology Effect of Na2Ti3O7 Nanoarrays on Sodium-Ion Storage.

Na2Ti3O7-based anodes show great promise for Na+ storage in sodium-ion batteries (SIBs), though the effect of Na2Ti3O7 morphology on battery performance remains poorly understood. Herein, hydrothermal syntheses is used to prepare free-standing Na2Ti3O7 nanosheets or Na2Ti3O7 nanotubes on Ti foil substrates, with the structural and electrochemical properties of the resulting electrodes explored in detail. Results show that the Na2Ti3O7 nanosheet electrode (NTO NSs) delivered superior performance in terms of reversible capacity, rate capability, and especially long-term durability in SIBs compared to its nanotube counterpart (NTO NTs). Electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations, combined with density functional theory calculations, demonstrated that the flexible 2D Na2Ti3O7 nanosheets are mechanically more robust than the rigid Na2Ti3O7 nanotube arrays during prolonged battery cycling, explaining the superior durability of the NTO NSs electrode. This work prompts the use of anodes based on Na2Ti3O7 nanosheets in the future development of high-performance SIBs.

Fabrication of PES Modified by TiO2/Na2Ti3O7 Nanocomposite Mixed-Matrix Woven Membrane for Enhanced Performance of Forward Osmosis: Influence of Membrane Orientation and Feed Solutions.

Water treatment is regarded as one of the essential elements of sustainability. To lower the cost of treatment, the wastewater volume is reduced via the osmotic process. Here, mixed-matrix woven forward osmosis (MMWFO) PES membranes modified by a TiO2/Na2Ti3O7 (TNT) nanocomposite were fabricated for treating water from different sources. Various techniques were used to characterize the TNT nanocomposite. The crystal structure of TNT is a mix of monoclinic Na2Ti3O7 and anorthic TiO2 with a preferred orientation of (2-11). The SEM image shows that the surface morphology of the TNT nanocomposite is a forked nano-fur with varying sizes regularly distributed throughout the sample. The impact of TNT wt.% on membrane surface morphologies, functional groups, hydrophilicity, and performance was investigated. Additionally, using distilled water (DW) as the feed solution (FS), the effects of various NaCl concentrations, draw solutions, and membrane orientations on the performance of the mixed-matrix membranes were tested. Different water samples obtained from various sources were treated as the FS using the optimized PES/TNT (0.01 wt.%) MMWFO membrane. Using textile effluent as the FS, the impact of various NaCl DS concentrations on the permeated water volume was investigated. The results show that the MMWFO membrane generated with the TNT nanocomposite at a 0.01 wt.% ratio performed better in FO mode. After 30 min of use with 1 M NaCl and various sources of water as the FS, the optimized MMWFO membrane provided a steady water flow and exhibited antifouling behavior. DW performed better than other water types whenever it was used owing to its greater flow (136 LMH) and volume reduction (52%). Tap water (TW), textile industrial wastewater (TIWW), gray water (GW), and municipal wastewater (MW) showed volume reductions of 41%, 34%, 33%, and 31.9%, respectively. Additionally, when utilizing NaCl as the DS and TIWW as the FS, 1 M NaCl resulted in more permeated water than 0.25 M and 0.5 M, yet a higher volume reduction of 41% was obtained.

Long-Cycle-Life Sodium-Ion Battery Fabrication via a Unique Chemical Bonding Interface Mechanism.

Titanates have been widely reported as anode materials for sodium-ion batteries (SIBs). However, their wide temperature suitability and cycle life remain fundamental issues that hinder their practical application. Herein, a novel hollow Na2 Ti3 O7 microsphere (H-NTO) with a unique chemically bonded NTO/C(N) interface is reported. Theoretical calculations demonstrated that the NTO/C(N) interface stabilizes the crystal structure, and the optimized interface enables the H-NTO anode to stably operate for 80 000 cycles in a conventional ester electrolyte with negligible capacity loss. Optimizing the electrolyte allows the H-NTO electrode to cycle stably for 200 calendar days without capacity degradation at -40 °C. The excellent cycling stability is attributed to the NTO/C(N) interface and the stable solid electrolyte interphase formed by the highly adaptable electrolyte/electrode interface. Titanate exhibits solvent co-intercalation behavior in ether-based electrolytes, and its robust structure ensures that it can adapt to large volume changes at low temperatures. This study provides a unique perspective on the long-cycle mechanism of titanate anodes and highlights the critical importance of manipulating the interfacial chemistry in SIBs, including the material and electrode/electrolyte interfaces.

A Flexible Humidity Sensor with Wide Range, High Linearity, and Fast Response Based on Ultralong Na2Ti3O7 Nanowires.

A flexible humidity sensor with wide sensing range, superior sensitivity, high linearity, and advanced response/recovery capabilities is extremely desirable for practical applications in human body-related (HBR) monitoring and human-machine interaction (HMI). However, the practical sensor lacks a versatile nanomaterial integrated with sensing capabilities and mechanical flexibility to meet the criteria. Herein, a comprehensive flexible humidity sensor with ultralong Na2Ti3O7 nanowires (>120 µm) is subtly constructed for the first time. Owing to the distinguish nanowires network structure, the sensor exhibits wide sensing range (11-95% RH), high sensitivity (>103), high linearity (R2 > 0.98), and fast response/recovery capability (8.9/2.1 s), as well as excellent respiratory stability (>5000 s). In addition, the Na2Ti3O7-based humidity sensor demonstrates superior flexibility and antibacteria capabilities, and exhibits diverse applications in respiration monitoring, noncontact detection, as well as dynamic interactive display. This work provides a multifunctional humidity sensor with excellent practicability, suggesting the great potential in next-generation human-related flexible/wearable devices.

Bismuth oxyhalide quantum dots modified sodium titanate necklaces with exceptional population of oxygen vacancies and photocatalytic activity.

We here demonstrate the controlled synthesis of BiOBr quantum dots (QDs) decorated Na2Ti3O7 necklaces via a hydrothermal transformation of sodium titanate nanotubes. The BiOBr QDs are deposited on the surface of Na2Ti3O7 necklaces, forming a heterogeneous interface of BiOBr(200) and Na2Ti3O7(110), which promotes the separation efficiency of photogenerated charges, thus resulting in its superior catalytic performance in the photo-oxidation of benzyl alcohol. The BiOBr/Na2Ti3O7-1.0 exhibiting highest oxygen defect population gives best photocatalytic activity with a promising conversion rate of 3.32 mmolreacted BA gcatal.-1h-1, which is substantially higher than the corresponding reported photocatalysts. DFT results corroborate the superior performance of BiOBr/Na2Ti3O7 is mainly due to the formation of a built-in electric field and given efficiently the charge transfer between BiOBr(200) and Na2Ti3O7(110). In all, this study reports a simple in-situ hydrothermal growth protocol to efficiently construct BiOBr/Na2Ti3O7 heterojunction composites and offers guidelines for design of a new synthetic strategy to prepare efficient photocatalysts.

Surface Engineering Strategy Using Urea To Improve the Rate Performance of Na2 Ti3 O7 in Na-Ion Batteries.

Na2 Ti3 O7 (NTO) is considered a promising anode material for Na-ion batteries due to its layered structure with an open framework and low and safe average operating voltage of 0.3 V vs. Na+ /Na. However, its poor electronic conductivity needs to be addressed to make this material attractive for practical applications among other anode choices. Here, we report a safe, controllable and affordable method using urea that significantly improves the rate performance of NTO by producing surface defects such as oxygen vacancies and hydroxyl groups, and the secondary phase Na2 Ti6 O13 . The enhanced electrochemical performance agrees with the higher Na+ ion diffusion coefficient, higher charge carrier density and reduced bandgap observed in these samples, without the need of nanosizing and/or complex synthetic strategies. A comprehensive study using a combination of diffraction, microscopic, spectroscopic and electrochemical techniques supported by computational studies based on DFT calculations, was carried out to understand the effects of this treatment on the surface, chemistry and electronic and charge storage properties of NTO. This study underscores the benefits of using urea as a strategy for enhancing the charge storage properties of NTO and thus, unfolding the potential of this material in practical energy storage applications.

(001) Facet-Dominated Hierarchically Hollow Na2Ti3O7 as a High-Rate Anode Material for Sodium-Ion Capacitors.

Sodium-ion capacitors (SICs) have shown great potential to combine the merits of high-power capability of traditional capacitors and high energy capability of batteries. However, the sluggish kinetics and inferior stability of conventional sodium-ion storage anode materials are major challenges for the practical utilization of SICs. In this work, interconnected urchin-like hollow Na2Ti3O7 (Na2Ti3O7-IcUH) chains were designed and prepared by a simple one-step template-assisting method. Through a variety of controlled experiments, we explored how to effectively engineer the crystal-oriented growth and string the urchin-like spheres together. Benefiting from its urchin-like hollow structure and fully exposed (001) facet, the resulting Na2Ti3O7-IcUH exhibits a superior rate capability of 96.2 mA h g-1 at 5 A g-1. Meanwhile, the interconnected three-dimensional primary structure endows Na2Ti3O7-IcUH with excellent cyclic stability (15% capacity loss at 5 A g-1 after 2000 cycles). By coupling with commercial active carbon, the assembled SIC successfully demonstrates a energy density of 134.3 W h kg-1 at a power density of 125 W kg-1 and 38.2 W h kg-1 at a high-power density of 2500 W kg-1, as well as a superior capacity retention of 75% after 2000 cycles at 2 A g-1 within 1-4 V.

Na+-Conductive Na2Ti3O7-Modified P2-type Na2/3Ni1/3Mn2/3O2 via a Smart in Situ Coating Approach: Suppressing Na+/Vacancy Ordering and P2-O2 Phase Transition.

Sodium-ion batteries (SIBs) have shown great superiority for grid-scale storage applications because of their low cost and the abundance of sodium. P2-type Na2/3Ni1/3Mn2/3O2 cathode materials have attracted much attention for their high capacities and operating voltages as well as their simple synthesis processes. However, Na+/vacancy ordering and the P2-O2 phase transition are unavoidable during Na+ insertion/extraction, leading to undesired voltage plateaus and deficient battery performances. We show that this defect can be effectually eliminated by coating a moderate Na+ conductor Na2Ti3O7 with a smart in situ coating approach and a concomitant doping of Ti4+ into the bulk structure. Based on the combined analysis of ex situ X-ray diffraction, scanning electron microscopy, electrochemical performance tests, and electrochemical kinetic analyses, Na2Ti3O7 coating and Ti4+ doping effectively refrain Na+/vacancy ordering and P2-O2 phase transition during cycling. Additionally, the Na2Ti3O7 coating layer suppresses particle exfoliation and accelerates Na+ diffusion at the cathode and electrolyte interface. Hence, Na2Ti3O7-coated Na2/3Ni1/3Mn2/3O2 exhibits excellent cycling stability (almost no capacity decay after 200 cycles at 5 C) and outstanding rate capability (31.1% of the initial capacity at a high rate of 5 C compared to only 10.4% for the pristine electrode). This coating strategy can provide a new guide for the design of prominent cathode materials for SIBs that are suitable for practical applications.

Effects of F-Doping on the Electrochemical Performance of Na2Ti3O7 as an Anode for Sodium-Ion Batteries.

The effects of fluorine (F) doping on the phase, crystal structure, and electrochemical performance of Na2Ti3O7 are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurements. F-doping does not change the crystal structure of NTO, although it has an effect on the morphology of the resultant product. As an anode material for sodium-ion batteries, the specific capacity of Na2Ti3O7 exhibits a 30% increase with F-doping owing to the improved sodium ion diffusion coefficient. F-doped Na2Ti3O7 also displays an enhanced rate capability and favourable cycling performance for more than 800 cycles.

Black Phosphorus Stabilizing Na2Ti3O7/C Each Other with an Improved Electrochemical Property for Sodium-Ion Storage.

Sodium-ion batteries have increasingly been considered as an attractive alternative to lithium-ion batteries for large-scale applications. High specific capacity and suitable working potential anode materials are one of the keys to search for future developments. Here, a novel and stable sodium titanate/carbon-black phosphorus (NTO/C-BP) hybrids are first fabricated as a promising anode material for advanced sodium-ion batteries. Under the protection of argon (Ar) atmosphere, the direct high-energy mechanical milling of the BP nanoparticle and NTO/C results in the formation of NTO/C-BP hybrids. In other words, the BP nanoparticle can be interconnected with bare NTO by P-O-Ti bonds and/or form stable P-C bonds with the carbon coating layer on the surface of NTO. The NTO/C-BP hybrids are not only beneficial for enhancing specific capacity but also have a great protective effect on the exposure of BP to air by the synergistic effect between BP and NTO/C. The results show that the NTO/C-BP hybrids can deliver very high specific capacity (∼225 mA h g-1 after 55 cycles at 20 mA g-1, ∼183 mA h g-1 after 100 cycles at 100 mA g-1). It is expected from these scientific findings that forming stable P-C bonds and P-O-Ti bonds in this work can serve as a guidance to other Ti-based and P-based electrode materials for practical large-scale application of sodium-ion batteries.

Hydrogenated Na2Ti3O7 Epitaxially Grown on Flexible N-Doped Carbon Sponge for Potassium-Ion Batteries.

With its inherent zig-zag layered structure and open framework, Na2Ti3O7 (NTO) is a promising anode material for potassium-ion batteries (KIBs). However, its poor electronic conductivity caused by large band gap (∼3.7 eV) usually leads to low-performance KIBs. In this work, we synthesize the fluff-like hydrogenated Na2Ti3O7 (HNTO) nanowires grown on N-doped carbon sponge (CS) as a binder-free and current-collector-free flexible anode for KIBs (denoted as HNTO/CS). High-resolution X-ray photoelectron spectroscopy (XPS) and electron spin-resonance spectroscopy (ESR) confirm the existence of Ti-OHs and O vacancies in HNTO. The first-principles calculation discloses that both Ti-OHs and O vacancies are equivalent to n-type doping because they can shift the Fermi level up to the conduction band, thus leading to a higher electronic conductivity and better performance for KIBs. In addition, the N-doped CS can further reinforce the conductivity and avoid the aggregation of HNTO nanowires during cycling. As a result, the as-made HNTO/CS can deliver a capacity of 107.8 mAh g-1 at 100 mA g-1 after 20 cycles, and keep the capacity of 90.9% and 82.5% after 200 and 1555 cycles, respectively, much better than the samples without hydrogenation treatment or N-doped CS and reported KTi xO y-based materials. Our work highlights the importance of hydrogenation treatment and N-doped CS in enhancing the electrochemical property for KIBs.

Composition and evolution of the solid-electrolyte interphase in Na2Ti3O7 electrodes for Na-ion batteries: XPS and Auger parameter analysis.

Na2Ti3O7 is considered a promising negative electrode for Na-ion batteries; however, poor capacity retention has been reported and the stability of the solid-electrolyte interphase (SEI) could be one of the main actors of this underperformance. The composition and evolution of the SEI in Na2Ti3O7 electrodes is hereby studied by means of X-ray photoelectron spectroscopy (XPS). To overcome typical XPS limitations in the photoelectron energy assignments, the analysis of the Auger parameter is here proposed for the first time in battery materials characterization. We have found that the electrode/electrolyte interface formed upon discharge, mostly composed by carbonates and semicarbonates (Na2CO3, NaCO3R), fluorides (NaF), chlorides (NaCl) and poly(ethylene oxide)s, is unstable upon electrochemical cycling. Additionally, solid state nuclear magnetic resonance (NMR) studies prove the reaction of the polyvinylidene difluoride (PVdF) binder with sodium. The powerful approach used in this work, namely Auger parameter study, enables us to correctly determine the composition of the electrode surface layer without any interference from surface charging or absolute binding energy calibration effects. As a result, the suitability for Na-ion batteries of binders and electrolytes widely used for Li-ion batteries is questioned here.