Crystallization of amorphous anodized TiO2 nanotube arrays.

Anodized TiO2 nanotube arrays (TNTAs) prepared by anodization have garnered widespread attention due to their unique structure and properties. In this study, we prepared TNTAs of varying lengths by controlling the anodization time. Among them, the nanotubes anodized for 2 h have an inner diameter of approximately 92 nm and a wall thickness of approximately 12 nm. Then we subjected amorphous TNTAs prepared by the anodization method to annealing treatments, systematically analyzing the evolution of morphology and structure with varying annealing temperatures. As the annealing temperature increases, the amorphous successively undergoes transitions to the anatase phase and then to the rutile phase. During the transition to the anatase phase, the structure of the nanotube array remains intact, with the complete preservation of the tubular array structure. However, during the transition to the rutile phase, the tubular array structure is destroyed. To address why the tubular array remains undamaged during the amorphous-to-anatase transition, we subjected amorphous TNTAs to annealing at 300 °C for different durations. Raman spectroscopy was employed for fit analysis, providing insights into the evolution of the molecular structure during the anatase phase transition. Finally, TNTAs annealed at different temperatures were incorporated into lithium-ion batteries. By combining XRD for semi-quantitative phase content and anatase particle size calculations, we established a correlation between structure and electrochemical performance. The results indicate a significant improvement in electrochemical performance for an amorphous-anatase structure obtained through annealing at 300 °C, providing insights for the design of high-performance energy storage materials.

Machine learning for data-driven design of high-safety lithium metal anode.

Here, we present a protocol for developing an inorganic-organic hybrid interphase layer using the self-assembled monolayers technique to enhance the surface of the lithium metal anode. We describe steps for extracting organic molecules from open-sourced databases and calculating their microscopic properties. We then detail procedures for developing a machine learning model for predicting the ionic diffusion barrier and preparing the inputs for prediction. This protocol enables a cost-effective workflow to identify promising self-assembled monolayers with exceptional performance. For complete details on the use and execution of this protocol, please refer to Zhang et al. (2023).1.

Spontaneous Built-In Electric Field in C3 N4 -CoSe2 Modified Multifunctional Separator with Accelerating Sulfur Evolution Kinetics and Li Deposition for Lithium-Sulfur Batteries.

The discovery of the heterostructures that is combining two materials with different properties has brought new opportunities for the development of lithium sulfur batteries (LSBs). Here, C3 N4 -CoSe2 composite is elaborately designed and used as a functional coating on the LSBs separator. The abundant chemisorption sites of C3 N4 -CoSe2 form chemical bonding with polysulfides, provides suitable adsorption energy for lithium polysulfides (LiPSs). More importantly, the spontaneously formed internal electric field accelerates the charge flow in the C3 N4 -CoSe2 interface, thus facilitating the transport of LiPSs and electrons and promoting the bidirectional conversion of sulfur. Meanwhile, the lithiophilic C3 N4 -CoSe2 sample with catalytic activity can effectively regulate the uniform distribution of lithium when Li+ penetrates the separator, avoiding the formation of lithium dendrites in the lithium (Li) metal anode. Therefore, LSBs based on C3 N4 -CoSe2 functionalized membranes exhibit a stable long cycle life at 1C (with capacity decay of 0.0819% per cycle) and a large areal capacity of 10.30 mAh cm-2 at 0.1C (sulfur load: 8.26 mg cm-2 , lean electrolyte 5.4 µL mgs -1 ). Even under high-temperature conditions of 60 °C, a capacity retention rate of 81.8% after 100 cycles at 1 C current density is maintained.

Monomicelle-Directed Engineering of Strained Carbon Nanoribbons as Oxygen Reduction Catalyst.

To date, precisely tailoring local active sites of well-defined earth-abundant metal-free carbon-based electrocatalysts for attractive electrocatalytic oxygen reduction reaction (ORR), remains challenging. Herein, the authors successfully introduce a strain effect on active C-C bonds adjacent to edged graphitic nitrogen (N), which raises appropriate spin-polarization and charge density of carbon active sites and kinetically favor the facilitation of O2 adsorption and the activation of O-containing intermediates. Thus, the constructed metal-free carbon nanoribbons (CNRs-C) with high-curved edges exhibit outstanding ORR activity with half-wave potentials of 0.78 and 0.9 V in 0.5 m H2 SO4 and 0.1 m KOH, respectively, overwhelming the planar one (0.52 and 0.81 V) and the N-doped carbon sheet (0.41 and 0.71 V). Especially in acidic media, the kinetic current density (Jk ) is 18 times higher than that of the planar one and the N-doped carbon sheet. Notably, these findings show the spin polarization of the asymmetric structure by introducing a strain effect on the C-C bonds for boosting ORR.

Recent advances in developing multiscale descriptor approach for the design of oxygen redox electrocatalysts.

Oxygen redox electrocatalysis is the crucial electrode reaction among new-era energy sources. The prerequisite to rationally design an ideal electrocatalyst is accurately identifying the structure-activity relationship based on the so-called descriptors which link the catalytic performance with structural properties. However, the quick discovery of those descriptors remains challenging. In recent, the high-throughput computing and machine learning methods were identified to present great prospects for accelerating the screening of descriptors. That new research paradigm improves cognition in the way of oxygen evolution reaction/oxygen reduction reaction activity descriptor and reinforces the understanding of intrinsic physical and chemical features in the electrocatalytic process from a multiscale perspective. This review summarizes those new research paradigms for screening multiscale descriptors, especially from atomic scale to cluster mesoscale and bulk macroscale. The development of descriptors from traditional intermediate to eigen feature parameters has been addressed which provides guidance for the intelligent design of new energy materials.

Construction of the Fast Potassiation Path in Sbx Bi1-x @NC Anode with Ultrahigh Cycling Stability for Potassium-Ion Batteries.

Due to the scarce of lithium resources, potassium-ion batteries (PIBs) have attracted extensive attention due to their similar electrochemical properties to lithium-ion batteries (LIBs) and more abundant potassium resources. Even though there is considerable progress in SbBi alloy anode for LIBs and PIBs, most studies are focused on the morphology/structure tuning, while the inherent physical features of alloy composition's effect on the electrochemical performance are rarely investigated. Herein, combined the nanonization, carbon compounding, and alloying with composition regulation, the anode of nitrogen-doped carbon-coated Sbx Bi1-x (Sbx Bi1-x @NC) with a series of tuned chemical compositions is designed as an ideal model. The density functional theory (DFT) calculation and experimental investigation results show that the K+ diffusion barrier is lower and the path is easier to carry out when element Bi dominates the potassiation reaction, which is also the reason for better circulation. The optimized Sb0.25 Bi0.75 @NC shows an excellent cycling performance with a reversible specific capacity of 301.9 mA h g-1 after 500 cycles at 0.1 A g-1 . Meanwhile, the charge-discharge mechanism is intuitively invetigated and analyzed by in situ X-ray diffraction (XRD) and transmission electron microscopy (TEM) in detail. Such an alloy-type anode synthesis approach and in situ observation method provide an adjustable strategy for the designing and investigating of PIB anodes.

Origin of oxygen-redox and transition metals dissolution in Ni-rich LixNi0.8Co0.1Mn0.1O2 cathode.

Recently, Ni-rich LiNixCoyMn1-x-yO2 (x ≥ 0.8) draw significant research attention as cathode materials in lithium-ion batteries due to their superiority in energy density. However, the oxygen release and the transition metals (TMs) dissolution during the (dis)charging process lead to serious safety issues and capacity loss, which highly prevent its application. In this work, we systematically explored the stability of lattice oxygen and TM sites in LiNi0.8Co0.1Mn0.1O2(NCM811) cathode via investigating various vacancy formations during lithiation/delithiation, and properties such as the number of unpaired spins (NUS), net charges, and d band center were comprehensively studied. In the process of delithiation (x = 1 → 0.75 → 0), the vacancy formation energy of lattice oxygen [Evac(O)] has been identified to follow the order of Evac(O-Mn) > Evac(O-Co) > Evac(O-Ni), and Evac(TMs) shows a consistent trend with the sequence of Evac(Mn) > Evac(Co) > Evac(Ni), demonstrating the importance of Mn to stabilize the structural skeleton. Furthermore, the |NUS| and net charge are proved to be good descriptors for measuring Evac(O/TMs), which show linear correlations with Evac(O) and Evac(TMs), respectively. Li vacancy plays a pivotal role on Evac(O/TMs). Evac(O/TMs) at x = 0.75 vary extremely between the NiCoMnO layer (NCM layer) and the NiO layer (Ni layer), which correlates well with |NUS| and net charge in the NCM layer but aggregates in a small region in the Ni layer due to the effect of Li vacancies. In general, this work provides an in-depth understanding of the instability of lattice oxygen and transition metal sites on the (104) surface of Ni-rich NCM811, which might give new insights into oxygen release and transition metal dissolution in this system.

Defect-Induced Dense Amorphous/Crystalline Heterophase Enables High-Rate and Ultrastable Sodium Storage.

Currently, the construction of amorphous/crystalline (A/C) heterophase has become an advanced strategy to modulate electronic and/or ionic behaviors and promote structural stability due to their concerted advantages. However, their different kinetics limit the synergistic effect. Further, their interaction functions and underlying mechanisms remain unclear. Here, a unique engineered defect-rich V2 O3 heterophase structure (donated as A/C-V2 O3- x @C-HMCS) composed of mesoporous oxygen-deficient amorphous - hollow core (A-V2 O3- x /HMC) and lattice-distorted crystalline shell (C-V2 O3 /S) encapsulated by carbon is rationally designed via a facile approach. Comprehensive density functional theory (DFT) calculations disclose that the lattice distortion enlarges the porous channels for Na+ diffusion in the crystalline phase, thereby optimizing its kinetics to be compatible with the oxygen-vacancy-rich amorphous phase. This significantly reduces the high contrast of the kinetic properties between the crystalline and amorphous phases in A/C-V2 O3- x @C-HMCS and induces the formation of highly dense A/C interfaces with a strong synergistic effect. As a result, the dense heterointerface effectively optimizes the Na+ adsorption energy and lowers the diffusion barrier, thus accelerating the overall kinetics of A/C-V2 O3- x @C-HMCS. In contrast, the perfect heterophase (defects-free) A/C-V2 O3 @C-HCS demonstrates sparse A/C interfacial sites with limited synergistic effect and sluggish kinetics. As expected, the A/C-V2 O3- x @C-HMCS achieves a high rate and ultrastable performance (192 mAh g-1 over 6000 cycles at 10 A g-1 ) when employed for the first time as a cathode for sodium-ion batteries (SIBs). This work provides general guidance for realizing dense heterophase cathode design for high-performance SIBs and beyond.

Alkaline Tolerant Antifreezing Additive Enabling Aqueous Zn||Ni Battery Operating at -60 °C.

Alkaline aqueous batteries such as the Zn||Ni batteries have attracted substantial interests due to their merits of high energy density, high safety and low cost. However, the freeze of aqueous electrolyte and the poor cycling stability in alkaline condition have hindered their operation in subzero conditions. Herein, we construct a stable aqueous electrolyte with lowest freezing point down to -90 °C by adding dimethyl sulfoxide (DMSO) as alkaline tolerant antifreezing additive into 1 M KOH solution. Meanwhile, we find the DMSO can also retard Zn anode corrosion and prevent Zn dendrite formation in alkaline condition, which enables the Zn plating/stripping over 700 h cycle at 1 mA cm-2 and 0.5 mAh cm-2 . The fabricated Zn||Ni battery can endure low working temperature even down to -60 °C and its dischage capacity retains 84.1 % at -40 °C, 60.6 % at -60 °C at 0.5 C. Meanwhile, it can maintain 600 cycles with a specific capacity retention of 86.5 % at -40 °C at 2 C.

Smart Materials Prediction: Applying Machine Learning to Lithium Solid-State Electrolyte.

Traditionally, the discovery of new materials has often depended on scholars' computational and experimental experience. The traditional trial-and-error methods require many resources and computing time. Due to new materials' properties becoming more complex, it is difficult to predict and identify new materials only by general knowledge and experience. Material prediction tools based on machine learning (ML) have been successfully applied to various materials fields; they are beneficial for modeling and accelerating the prediction process for materials that cannot be accurately predicted. However, the obstacles of disciplinary span led to many scholars in materials not having complete knowledge of data-driven materials science methods. This paper provides an overview of the general process of ML applied to materials prediction and uses solid-state electrolytes (SSE) as an example. Recent approaches and specific applications to ML in the materials field and the requirements for building ML models for predicting lithium SSE are reviewed. Finally, some current obstacles to applying ML in materials prediction and prospects are described with the expectation that more materials scholars will be aware of the application of ML in materials prediction.

Influence of Fluorine Substitution on the Photovoltaic Performance of Wide Band Gap Polymer Donors for Polymer Solar Cells.

The design and development of wide band gap (WBG) polymer donors are critical for achieving high power conversion efficiencies (PCEs) in polymer solar cells. In this work, four WBG polymer donors, Q4, Q5, Q6, and Q7, with different numbers and positions of fluorine substitution (n = 0, 2, 2, and 4, respectively) were prepared, and the effect of fluorination on their photovoltaic performance was systematically investigated. When blended with a small-molecule electron acceptor MeIC, the devices based on Q4, Q5, Q6, and Q7 showed PCEs of 10.34, 11.06, 5.26, and 0.48%, respectively. When coupled with a low band gap polymer acceptor PYIT to fabricate all-polymer solar cells (all-PSCs), while the other three polymers (Q5-Q7) exhibited much lower PCEs in the range of 0.12-6.71%, the Q4 polymer-based all-PSCs showed the highest PCE of 15.06%, comparable to that of the devices fabricated with the star polymer donor PM6 (PCE = 15.00%). Detailed physicochemical and morphological studies revealed that an over-substitution of F in Q7 results in undesired low-lying HOMO levels and phase separation with the acceptors, thus resulting in its inferior PCEs. Moreover, the less F-substitution and controlling of the positions of F-substitution position in Q4 and Q5 can improve the HOMO energy level matching as well as morphologies between these two polymers with the acceptors, which in turn gives rise to higher performances. Clearly, our results indicate that Q4 is a promising donor candidate for high-performance all-PSCs, and the fine-tuning of both the number and positions of F-substitution in the polymer backbone is essential in developing high-performance WBG polymer donors.

Omni-functional crystal: Advanced methods to characterize the composition and homogeneity of lithium niobate melts and crystals.

Lithium niobate (LN) is a type of multifunctional dielectric and ferroelectric crystal that is widely used in acoustic, optical, and optoelectronic devices. The performance of pure and doped LN strongly depends on various factors, including its composition, microstructure, defects, domain, and homogeneity. The structure and composition homogeneity can affect both the chemical and physical properties of LN crystals, including their density, Curie temperature, refractive index, and piezoelectric and mechanical properties. In terms of practical demands, both the composition and microstructure characterizations these crystals must range from the nanometer scale up to the millimeter and wafer scales. Therefore, LN crystals require different characterization technologies when verifying their quality for various device applications. Optical, electrical, and acoustic technologies have been developed, including x-ray diffraction, Raman spectroscopy, electron microscopy, and interferometry. To obtain detailed structural information, advanced sub-nanometer technologies are required. For general industrial demands, fast and non-destructive technologies are preferable. This review outlines the advanced methods used to characterize both the composition and homogeneity of LN melts and crystals from the micro- to wafer scale.

Growth and Optical Properties of the Whole System of Li(Mn1-x,Nix)PO4 (0 ≤ x ≤ 0.5) Single Crystals.

A series of single crystals of Li(Mn1-x,Nix)PO4 (x = 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.08, 0.10, 0.15, 0.20, and 0.50) have been grown to large sizes up to 5 mm in diameter and 120 mm in length using the floating zone method for the first time. The comprehensive characterizations of the as-grown crystals were performed before further physical property measurements. The composition of the grown crystals was determined by energy-dispersive X-ray spectroscopy. The crystal structures were characterized by the X-ray powder diffraction method with a GSAS fitting for structural refinement, which reveals a high phase purity of the as-obtained crystals. The polarized microscopic images and Laue patterns prove the excellent quality of the single crystals. Oriented cuboids with sizes of 2.7 × 3.8 × 2.1 mm3 along the a, b, and c crystalline directions were cut and polished for further anisotropic magnetic and transparent measurements. We also first proposed a new potential application in the non-linear optical (NLO) and laser generation application for LiMPO4 (M = transition metal) materials. The optical and laser properties, such as the absorption spectra and the second harmonic generation (SHG), have been investigated and have furthermore confirmed the good quality of the as-grown single crystals.

State of the Art in Crystallization of LiNbO3 and Their Applications.

Lithium niobate (LiNbO3) crystals are important dielectric and ferroelectric materials, which are widely used in acoustics, optic, and optoelectrical devices. The physical and chemical properties of LiNbO3 are dependent on microstructures, defects, compositions, and dimensions. In this review, we first discussed the crystal and defect structures of LiNbO3, then the crystallization of LiNbO3 single crystal, and the measuring methods of Li content were introduced to reveal reason of growing congruent LiNbO3 and variable Li/Nb ratios. Afterwards, this review provides a summary about traditional and non-traditional applications of LiNbO3 crystals. The development of rare earth doped LiNbO3 used in illumination, and fluorescence temperature sensing was reviewed. In addition to radio-frequency applications, surface acoustic wave devices applied in high temperature sensor and solid-state physics were discussed. Thanks to its properties of spontaneous ferroelectric polarization, and high chemical stability, LiNbO3 crystals showed enhanced performances in photoelectric detection, electrocatalysis, and battery. Furthermore, domain engineering, memristors, sensors, and harvesters with the use of LiNbO3 crystals were formulated. The review is concluded with an outlook of challenges and potential payoff for finding novel LiNbO3 applications.

2D Organic-Inorganic Hybrid Perovskite Quantum Well Materials and Their Dramatical X-ray Optoelectronic Properties.

Two-dimensional organic-inorganic hybrid perovskites (2D OIHPs) have attracted extensive attention in the field of X-ray detection due to their excellent stability compared to traditional three-dimensional OIHPs and the strong optoelectronic response to X-ray along the quantum wells. In this review, the nucleation and growth process as well as intermolecular forces for controlling out-of-plane growth are summarized along with the oriented growth mechanism. The optoelectronic properties in 2D OIHP under irradiation of X-ray are also discussed. Finally, conclusions and outlook for orientation 2D OIHP quantum wells and their challenges in application of direct X-ray detection are given. This review will provide a basic understanding on the strategy of designing 2D OIHP thick films as promising X-ray photoconductors, which may inspire the development of next-generation X-ray detectors.

Boosting the Efficiency of Non-fullerene Organic Solar Cells via a Simple Cathode Modification Method.

This work demonstrates a simple yet effective method to significantly improve the power conversion efficiency (PCE) of highly efficient non-fullerene organic solar cells by mixing two electron transport materials. The new electron transport layer shows an energy level better aligned with the active layer and an improved morphology that could reduce the active layer-electrode contact. These improvements lead to enhanced charge extraction, better charge selectivity, suppressed exciton recombination, and finally a boosted PCE in the PM6:Y6-based solar cells. When applied in conjunction with the non-halogenated solvent-processed PM6:PY-IT-based active layer, the mixed ETL also gives rise to a leading result for binary all-polymer solar cells (PCE of >16%) with a concurrent increase in VOC, JSC, and FF.

Multiscale Investigation into Chemically Stable NASICON Solid Electrolyte in Acidic Solutions.

Natrium superionic conductor (NASICON) solid electrolyte has been attracting wide attention due to its high ionic conductivity, low cost, and environmental friendliness. In this work, the chemical stability of the NASICON solid electrolyte with the composition of Na3Zr2Si2PO12 was evaluated in acidic solutions with different pH values, and the corrosion mechanism of the NASICON solid electrolyte was revealed at the multiscale level. Variations in bulk impedance, grain boundary impedance, and surface crack impedance with immersion time were determined by an AC impedance method. Comprehensive studies upon scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) etching, X-ray diffraction (XRD), and Raman spectroscopy, the morphological transformation, degradation limit depth, Cl- penetration effect, and proton exchange between H3O+ and Na+ were examined ranging from macro- and meso- to microscales, respectively. With the decrease of the pH of the solution, the exchange rate between H3O+ and Na+ protons increases. The lack of Na+ within the crystallographic lattice leads to the shrinkage of phosphorus-oxygen tetrahedra, which is the main reason for the decrease of unit cell volume, grain refinement, and surface cracks gradually. This work features multiscale characterizations of crystal structure, grain boundaries, surface morphology changes, and Na+ transport, which deepens our physicochemical understanding of solid electrolytes with high chemical stability.

Highly Ordered TiO2 Nanotube Arrays with Engineered Electrochemical Energy Storage Performances.

Nanoscale engineering of regular structured materials is immensely demanded in various scientific areas. In this work, vertically oriented TiO2 nanotube arrays were grown by self-organizing electrochemical anodization. The effects of different fluoride ion concentrations (0.2 and 0.5 wt% NH4F) and different anodization times (2, 5, 10 and 20 h) on the morphology of nanotubes were systematically studied in an organic electrolyte (glycol). The growth mechanisms of amorphous and anatase TiO2 nanotubes were also studied. Under optimized conditions, we obtained TiO2 nanotubes with tube diameters of 70-160 nm and tube lengths of 6.5-45 µm. Serving as free-standing and binder-free electrodes, the kinetic, capacity, and stability performances of TiO2 nanotubes were tested as lithium-ion battery anodes. This work provides a facile strategy for constructing self-organized materials with optimized functionalities for applications.

Perspective on Micro-Supercapacitors.

The rapid development of portable, wearable, and implantable electronic devices greatly stimulated the urgent demand for modern society for multifunctional and miniaturized electrochemical energy storage devices and their integrated microsystems. This article reviews material design and manufacturing technology in different micro-supercapacitors (MSCs) along with devices integrate to achieve the targets of their various applications in recent years. Finally, We also critically prospect the future development directions and challenges of MSCs.