Understanding Electrochemical Performance Enhancement with Quaternary NCMA Cathode Materials.

Ni-rich cathode materials show promise for use in lithium-ion batteries. However, a significant obstacle to their widespread adoption is the structural damage caused by microcracks. This research paper presents the synthesis of Ni-rich cathode materials, including LiNi0.8Co0.1Mn0.1O2 (referred to as NCM) and Li(Ni0.8Co0.1Mn0.1)0.98Al0.02O2 (referred to as NCMA), achieved through the high-temperature solid-phase method. Electrochemical (EC) testing results reveal the impressive EC performance of NCMA. NCMA exhibited a discharge capacity of 141.6 mAh g-1 and maintained a cycle retention rate of up to 74.92% after 300 cycles at a 1 C rate. In contrast, the NCM had a discharge capacity of 109.7 mAh g-1 and a cycle retention rate of 61.22%. Atomic force microscopy showed that the Derjaguin-Muller-Toporov (DMT) modulus value of NCMA exceeded that of NCM, signifying a greater mechanical strength of NCMA. Density functional theory calculations demonstrated that the addition of aluminum during the delithiation process led to the mitigation of anisotropic lattice changes and the stabilization of the NCMA structure. This improvement was attributed to the relatively stronger Al-O bonds compared to the Ni(Co, Mn)-O bonds, which reduced the formation of microcracks by enhancing NCMA's mechanical strength.

Density Functional Theory Investigation on the Nitrogen Reduction Mechanism in Two-Dimensional Transition-Metal Boride with Ordered Metal Vacancies.

The creation of ordered collective vacancies in experiment proves challenging within a two-dimensional lattice, resulting in a limited understanding of their impact on catalyst performance. Motivated by the successful experimental synthesis of monolayer molybdenum borides with precisely ordered metal vacancies [Zhou et al. Science 2021, 373, 801-805] through dealloying, the nitrogen reduction reaction (NRR) in monolayer borides was systematically investigated to elucidate the influence of such ordered metal vacancies on catalytic reactions and the underlying mechanisms. The results reveal that the N-containing intermediates tend to dissociate, facilitating the NRR process with reduced UL. The emergence of ordered metal vacancies modulates the electronic properties of the catalyst and partially facilitates the decomposition of N-containing intermediates. However, the UL for NRR in Mo4/3B2 and W4/3B2 exhibits a significant increase. The compromised electrochemical performance is explained through the development of a simple electronic descriptor of the d-p band center (ΔdM-pB). Among these materials, Mo4/3Sc2/3B2 exhibits the most superior catalytic activity with a UL of -0.5 V and favorable NRR selectivity over the HER. Our results provide mechanistic insights into the role of ordered metal vacancies in transition-metal boride for the NRR and highlight a novel avenue toward the rational design of superior NRR catalysts.

Conductive Polymer Coated Layered Double Hydroxide as a Novel Sulfur Reservoir for Flexible Lithium-Sulfur Batteries.

Lithium-sulfur battery (LSB) is widely regarded as the most promising next-generation energy storage system owing to its high theoretical capacity and low cost. However, the practical application of LSBs is mainly hampered by the low electronic conductivity of the sulfur cathode and the notorious "shuttle effect", which lead to high voltage polarization, severe over-charge behavior, and rapid capacity decay. To address these issues, a novel sulfur reservoir is synthesized by coating polypyrrole (PPy) thin film on hollow layered double hydroxide (LDH) (PPy@LDH). After compositing with sulfur, such PPy@LDH-S cathode shows a multi-functional effect to reserve lithium polysulfides (LiPSs). In addition, the unique architecture provides sufficient inner space to encapsulate the volume expansion and enhances the reaction kinetics of sulfur-based redox chemistry. Theoretical calculations have illustrated that the PPy@LDH has shown stronger chemical adsorption capability for LiPSs than those of porous carbon and LDH, preventing the shuttling of LiPSs and enhancing the nucleation affinity of liquid-solid conversion. As a result, the PPy@LDH-S electrode delivers a stable cycling performance and a superior rate capability. Flexible battery has demonstrated this PPy@LDH-S electrode can work properly with treatments of bending, folding, and even twisting, paving the way for wearable devices and flexible electronics.

First principles investigation on Na-ion storage in two-dimensional boron-rich B2N, B3N, and B5N.

Na-ion batteries (SIBs) are emerging as a promising alternative to Li-ion batteries for large-scale energy storage in light of abundant Na resources and their low cost. Development of appropriate electrode materials that can conquer some critical issues such as low theoretical storage capacity and sluggish redox kinetics resulting from the larger radius of Na is urgently needed for their practical applications. In this work, boron-rich 2D BxN (x = 2, 3, and 5) has been explored as promising anode materials for high-performance SIBs based on density functional theory calculations. BxN electrodes exhibit moderate affinity toward Na-ions with adsorption energies of -0.41 to -1.21 eV, which allows stable Na-ion intercalation without the formation of metal dendrites. Moreover, both B3N and B5N deliver low diffusion barriers (0.28 and 0.08 eV) for Na-ion migration, guaranteeing a high charging/discharging rate. More importantly, these BxN anodes exhibit not only a remarkably high theoretical capacity of 1129-1313 mA h g-1 but also a low open-circuit voltage (0.45-0.87 V), which is important to achieve high energy density. AIMD simulations have confirmed the excellent cyclability of BxN electrodes during reversible lithiation/delithiation. These results suggested that the BxN electrode could be used as a new lightweight SIB anode with high capacity, cyclability, and desired rate performance.

Prediction of a planar BxP monolayer with inherent metallicity and its potential as an anode material for Na and K-ion batteries: a first-principles study.

Borophene, the lightest two-dimensional material, exhibits exceptional storage capacity as an anode material for sodium-ion batteries (NIBs) and potassium-ion batteries (PIBs). However, the pronounced surface activity gives rise to strong interfacial bonding between borophene and the metal substrate it grows on. Incorporation of heterogeneous atoms capable of forming strong bonds with boron to increase borophene stability while preserving its intrinsic metallic conductivity and high theoretical capacity remains a great challenge. In this study, a particle swarm optimization (PSO) method was employed to determine several new two-dimensional monolayer boron phosphides (BxP, x = 3-6) with rich boron components. The obtained BxP has great potential to be used as an anode material for sodium-ion batteries/potassium-ion batteries (SIBs/PIBs), according to DFT calculations. BxP demonstrates remarkable stability compared with borophene which ensures their feasibility of experimental synthesis. Moreover, B5P and B6P exhibit high electronic conductivity and ionic conductivity, with migration energy barriers of 0.20 and 0.21 eV for Na ions and 0.07 eV for K ions. Moreover, the average open circuit voltage falls within a favorable range of 0.25-0.73 V, which results in a high storage capacity of 1119-2103 mA h g-1 for SIBs and 631-839 mA h g-1 for PIBs. This study paves the way for exploring boron-rich 2D electrode materials for energy applications and provides valuable insights into the functionalization and stabilization of borophene.

Ru- and Cl-Codoped Li3 V2 (PO4 )3 with Enhanced Performance for Lithium-Ion Batteries in a Wide Temperature Range.

Li3 V2 (PO4 )3 (LVP) is a promising cathode material for lithium-ion batteries, especially when used in a wide temperature range, due to its high intrinsic ionic mobility and theoretical capacity. Herein, Ru- and Cl-codoped Li3 V2 (PO4 )3 (LVP-Rux -Cl3 x ) coated with/without a nitrogen-doped carbon (NC) layer are synthesized. Among them, the optimized sample (LVP-Ru0.05 -Cl0.15 @NC) delivers remarkable performances at both room temperature and extreme temperatures (-40, 25, and 60 °C), indicating temperature adaptability. It achieves intriguing capacities (49 mAh g-1 at -40 °C, 128 mAh g-1 at 25 °C, and 123 mAh g-1 at 60 °C, all at 0.5 C), long cycle life (94% capacity retention after 2000 cycles at 25 °C and 5 C), and high-rate capabilities (up to 20 C). The structural evolution features and capacity loss mechanisms of LVP-Ru0.05 -Cl0.15 @NC are further investigated using in situ X-ray diffraction (XRD) at different temperatures (-10, 25, and 60 °C) during redox reactions. Theoretical calculations elucidate that Ru- and Cl-codoping can greatly improve the intrinsic diffusion coefficient of LVP by reducing its bandgap energy and lowering the energy barrier of lithium-ion diffusion. In "all-weather" conditions, the dual-element co-doping strategy is critical for increasing electrochemical performance.

Role of nonspherical DLVO and capillary forces in the transport of 2D delaminated Ti3C2Tx MXene in saturated and unsaturated porous media.

The transport and retention of two-dimensional (2D) nanomaterials, such as graphene oxide, in porous media have attracted lots of attention. However, previous studies often simplified these 2D colloids as equivalent spheres for numerical simulations, which ignored the influence of particle shape on colloid retention at multiple interfaces. In this study, a novel 2D nanomaterial delaminated Ti3C2Tx (d-Ti3C2Tx) was adopted to fill this knowledge gap. Comprehensive analyses of the 2D colloid retention mechanisms were conducted based on colloid characterization, saturated and unsaturated column experiments, reactive transport modeling, 2D-based DLVO and nonspherical capillary energy simulations. Results show that d-Ti3C2Tx mobility in both saturated and unsaturated conditions enhanced with the increase in pH and decrease in ionic strength. The DLVO interaction energy of d-Ti3C2Tx at the sand-water-interface (SWI) decreased with the orientation angle of the colloidal major axis to the sand surface from 0° to 90°. The primary mechanism under saturated flow conditions was the irreversible attachment in the deep secondary minimum at the SWI with the major axis of d-Ti3C2Tx parallel to the sand surface. The attachment in the primary minimum at 0° was impossible due to the extremely high energy barrier, and the attachment in the primary and secondary minimum at other orientation angles were negligible. d-Ti3C2Tx only experienced repulsive electrostatic force when approaching the air-water-interface (AWI) no matter the particle orientation. The detaching capillary potential energy was 3 orders of magnitude larger than the attractive DLVO interaction energy of the SWI in the secondary minimum at 0°, suggesting that the capillary force-induced irreversible attachment at the AWI was the primary mechanism under unsaturated flow conditions. This study shows that the DLVO and capillary potential energies were significantly dependent on the particle-interface orientation and colloidal shape. A simplification of 2D colloids as spheres is not recommended.

Rationalizing the Effect of Oxygen Vacancy on Oxygen Electrocatalysis in Li-O2 Battery.

Albeit the effectiveness of surface oxygen vacancy in improving oxygen redox reactions in Li-O2 battery, the underpinning reason behind this improvement remains ambiguous. Herein, the concentration of oxygen vacancy in spinel NiCo2 O4 is first regulated via magnetron sputtering and its relationship with catalytic activity is comprehensively studied in Li-O2 battery based on experiment and density functional theory (DFT) calculation. The positive effect posed by oxygen vacancy originates from the up shifted antibond orbital relative to Fermi level (Ef ), which provides extra electronic state around Ef , eventually enhancing oxygen adsorption and charge transfer during oxygen redox reactions. However, with excessive oxygen vacancy, the negative effect emerges because the metal ions are mostly reduced to low valence based on the electrical neutral principle, which not only destabilizes the crystal structure but also weakens the ability to capture electrons from the antibond orbit of Li2 O2 , leading to poor catalytic activity for oxygen evolution reaction (OER).

Cu-supported nitrogen-doped carbon nanofibers with hierarchical three-dimensional net structure as binder-free anodes for enhanced lithium-ion batteries.

Cu-supported nitrogen-doped carbon nanofibers (NCNFs) were fabricated via electrospinning and subsequent activation treatment with poly vinylpyrrolidone as both carbon and nitrogen sources. The NCNFs are firmly adhered to Cu foil without any additional binder and form a hierarchical three-dimensional net structure, which could effectively shorten the diffusion paths for electrons and lithium ions, thus resulting in lower impedance and superior electrochemical properties. Additionally, NCNFs feature a amorphous carbon structure, N-rich carbon lattice and wide pore distribution, not only ensuring fast ions/electrons transport, but also giving rise to the higher energy density. When directly used as a binder-free electrode, NCNFs deliver a high reversible capacity of 617.8 mAh g-1 at 200 mA g-1 after 100 cycles and maintain a superior capacity of 274.1 mAh g-1 at 1.44 A g-1 even after 500 cycles. Besides, the reversible capacity up to 216.5 mAh g-1 can be still obtained at a high current density of 6 A g-1, demonstrating the excellent high-rate cyclability. The facile synthesis approach and superior electrochemical properties make NCNFs electrodes an alternative anode candidate for lithium-ion batteries.

Ubiquitination of cGAS by TRAF6 regulates anti-DNA viral innate immune responses.

cGAS-STING (stimulator of interferon genes) signaling is crucial for the recognition of cytoplasmic double-stranded DNA by host cells and consequently activating innate immune response by promoting the production cGAMP and type I interferon. However, it remains elusive how the cGAS enzymatic activity is regulated dynamically. In this study, we identified TRAF6 as a regulator of cGAS mediated anti-viral innate immunity. Our data showed that either ectopic expression or knockdown of TRAF6 modulates the double strand DNA induced expression of interferon-responsive genes. Mechanistically, TRAF6 specifically promotes cGAS activation by targeting cGAS for ubiquitination. Knockdown of TRAF6 results in a decrease in cGAS-induced IFNß production when cells were infected with herpes simplex virus-1 (HSV-1). Together, our data identified TRAF6 as a positive regulator of cGAS-STING pathway by regulating cGAS activity.

Enhancement of lithium-ion hopping on halogen-doped χ3 borophene.

Borophenes, which are two-dimensional boron counterparts made of the three synthetic polymorphs T, ß12 and χ3, have been considered as potential anode materials in Li-ion batteries with extremely high capacities. However, Li hopping on ß12 and χ3 borophenes is quite slow with high energy barriers (around 0.6 eV), thus preventing the application of these borophenes in the fast charging realm. Here, we have used halogen functionalization in an attempt to boost the sluggish Li-ion diffusion dynamics in the prototype χ3 borophene system. Halogens bind strongly to χ3 borophene with substantial electron transfer from the latter to the former, thereby leading to local electron deficiency in the χ3 borophene. The synergy of electron extraction from χ3 borophene and the electrostatic attraction between halogens and Li results in an enhanced affinity between χ3 borophene and Li as well as a reduction in the Li-ion hopping barrier. Iodine is the preferred dopant, for which most diffusion paths exhibit energy barriers typically smaller than 0.2 eV. Our results suggest that halogen incorporation could facilitate intercalation and de-intercalation of Li-ions in borophene-based anode materials.

Reversible hydrogen storage in pristine and Li decorated 2D boron hydride.

Motived by the recent experimental fabrication of two-dimensional boron hydride (BH) sheets (Nishino et al., J. Am. Chem. Soc. 2017, 139, 13761), we explore the feasibility of pristine and Li doped BH sheets as a hydrogen storage medium within the framework of density functional theory. BH shows an unexpected high affinity to Li with a binding energy of -2.38 eV in comparison to other alkali and alkaline earth metals (Na, K, Ca, Mg and Al), much larger than its bulk cohesive energy (-1.63 eV). Energy barriers of Li diffusion on BH are also determined to be around 1.12 eV, showing both high dynamic and thermodynamic stability without the issue of cluster formation. Moreover, Li decorated BH is expected to achieve a high theoretical gravimetric density of 11.57 wt% with an average H2 adsorption energy of -0.17 eV, holding great potential in massive hydrogen storage. In addition to the storage, thermodynamic analysis on the desorption behaviors of H2 molecules is performed via N-P-T diagram, which demonstrates that most of the H2 molecules (8.30 wt%) could be released at 3 atm/100 °C. Thus, the Li-decorated BH sheets are expected to be applied as an efficient medium for hydrogen storage under ambient conditions.

Metallic borophene polytypes as lightweight anode materials for non-lithium-ion batteries.

Applications of rechargeable non-lithium-ion batteries (Na+, K+, Ca2+, Mg2+, and Al3+ NLIBs) are significantly hampered by the deficiency of suitable electrode materials. Searching for anode materials with desirable electrochemical performance is urgent for the large-scale energy storage demands of next generation renewable energy technologies. In this study, three types of recently synthesized borophenes are predicted to serve as high-performing anodes for NLIBs based on density functional theory. All the borophenes considered here are metallic with favorable in-plane stiffness. Dirac fermions were identified in two types of borophenes, guaranteeing their high electron mobility. Moreover, borophene configuration-dependent metal-ion migration, theoretical capacities, and open-circuit voltages were demonstrated with respect to the different adsorption behaviors and atom mass densities of anode materials. Our results provide insights into the configuration-dependent electrode performance of borophene and the corresponding metal-ion storage mechanism.

Sol-gel synthesis and luminescence property of Sr4 Al2 O7 :Re3+ ,R+ (Re = Eu and Dy; R = Li, Na and K) phosphors for white LEDs.

Sr4 Al2 O7 :Eu3+ and Sr4 Al2 O7 :Dy3+ phosphors with alkali metal substitution were prepared using a sol-gel method. The effects of a charge compensator R on the structure and luminescence of Sr4 Al2 O7 :Re3+ ,R+ (Re = Eu and Dy; R = Li, Na and K) phosphors were investigated in detail. Upon heating to 1400°C, the structure of the prepared samples was that of the standard phase of Sr4 Al2 O7 . Under ultraviolet excitation, all Sr4 Al2 O7 :Eu3+ ,R+ samples exhibited several narrow emission peaks ranging from 550 to 700 nm due to the 4f â†’ 4f transition of Eu3+ ions. All Sr4 Al2 O7 :Dy3+ ,R+ phosphors showed two emission peaks at 492 and 582 nm, due to the 4 F9/2  â†’ 6 H15/2 and 4 F9/2  â†’ 6 H13/2 transitions of Dy3+ ions, respectively. The luminescence intensity of Sr4 Al2 O7 :Re3+ ,R+ (Re = Eu and Dy; R = Li, Na and K) phosphors improved markedly upon the addition of charge compensators, promoting their application in white light-emitting diodes with a near-ultraviolet chip.

Performance evaluation of ML models for preoperative prediction of HER2-low BC based on CE-CBBCT radiomic features: A prospective study.

To explore the value of machine learning (ML) models based on contrast-enhanced cone-beam breast computed tomography (CE-CBBCT) radiomics features for the preoperative prediction of human epidermal growth factor receptor 2 (HER2)-low expression breast cancer (BC). Fifty-six patients with HER2-negative invasive BC who underwent preoperative CE-CBBCT were prospectively analyzed. Patients were randomly divided into training and validation cohorts at approximately 7:3. A total of 1046 quantitative radiomic features were extracted from CE-CBBCT images and normalized using z-scores. The Pearson correlation coefficient and recursive feature elimination were used to identify the optimal features. Six ML models were constructed based on the selected features: linear discriminant analysis (LDA), random forest (RF), support vector machine (SVM), logistic regression (LR), AdaBoost (AB), and decision tree (DT). To evaluate the performance of these models, receiver operating characteristic curves and area under the curve (AUC) were used. Seven features were selected as the optimal features for constructing the ML models. In the training cohort, the AUC values for SVM, LDA, RF, LR, AB, and DT were 0.984, 0.981, 1.000, 0.970, 1.000, and 1.000, respectively. In the validation cohort, the AUC values for the SVM, LDA, RF, LR, AB, and DT were 0.859, 0.880, 0.781, 0.880, 0.750, and 0.713, respectively. Among all ML models, the LDA and LR models demonstrated the best performance. The DeLong test showed that there were no significant differences among the receiver operating characteristic curves in all ML models in the training cohort (P > .05); however, in the validation cohort, the DeLong test showed that the differences between the AUCs of LDA and RF, AB, and DT were statistically significant (P = .037, .003, .046). The AUCs of LR and RF, AB, and DT were statistically significant (P = .023, .005, .030). Nevertheless, no statistically significant differences were observed when compared to the other ML models. ML models based on CE-CBBCT radiomics features achieved excellent performance in the preoperative prediction of HER2-low BC and could potentially serve as an effective tool to assist in precise and personalized targeted therapy.

Trade for Food Security: The Stability of Global Agricultural Trade Networks.

Global food production is facing increasing uncertainties under climate change and the coronavirus pandemic, provoking challenges and severe concerns to national food security. The role of global agricultural trade in bridging the imbalance between food supply and demand has come to the fore. However, the impact of multifaceted and dynamic factors, such as trade policies, national relations, and epidemics, on the stability of the agricultural trade network (ATN) needs to be better addressed. Quantitatively, this study estimated grouping characteristics and network stability by analyzing the changing global ATN from 1986 to 2018. We found that the evolution of global agricultural trade communities has gone through four stages: the dominance of the US-Asian community, the rise of the European-African community, the formation of tri-pillar communities, and the development of a multipolar community with a more complex structure. Despite witnessing a progressive increase in the nodal stability of the global ATN during the decades, particular gaps can still be found in stability across countries. Specifically, the European community achieved stability of 0.49 and its trade relations were effectively secured. Meanwhile, the remaining leading communities' stability shows a stable and upward trend, albeit with more significant challenges in trade relations among some of them. Therefore, how to guarantee the stability of trade relations and strengthen the global ATN to resist external shocks has become an essential question to safeguard global food security.

Salt Anion Amphiphilicity-Activated Electrolyte Cosolvent Selection Strategy toward Durable Zn Metal Anode.

One effective solution to inhibit side reactions and Zn dendrite growth in aqueous Zn-ion batteries is to add a cosolvent into the Zn(CF3SO3)2 electrolyte, which has the potential to form a robust solid electrolyte interface composed of ZnF2 and ZnS. Nevertheless, there is still a lack of discussion on a convenient selection method for cosolvents, which can directly reflect the interactions between solvent and solute to rationally design the electrolyte solvation structure. Herein, logP, where P is the octanol-water partition coefficient, a general parameter to describe the hydrophilicity and lipophilicity of chemicals, is proposed as a standard for selecting cosolvents for Zn(CF3SO3)2 electrolyte, which is demonstrated by testing seven different types of solvents. The solvent with a logP value similar to that of the salt anion CF3SO3- can interact with CF3SO3-, Zn2+, and H2O, leading to a reconstruction of the electrolyte solvation structure. To prove the concept, methyl acetate (MA) is demonstrated as an example due to its similar logP value to that of CF3SO3-. Both the experimental and theoretical results illustrate that MA molecules not only enter into the solvation shell of CF3SO3- but also coordinate with Zn2+ or H2O, forming an MA and CF3SO3- involved core-shell solvation structure. The special solvation structure reduces H2O activity and contributes to forming an anion-induced ZnCO3-ZnF2-rich solid electrolyte interface. As a result, the Zn||Zn cell and Zn||NaV3O8·1.5H2O cell with MA-involved electrolyte exhibit superior performances to that with the MA-free electrolyte. This work provides an insight into electrolyte design via salt anion chemistry for high-performance Zn batteries.

Selective catalytic oxidation of formaldehyde on single V- and Cr-atom decorated magnetic C4N3 substrate: A first principles study.

Formaldehyde (HCHO) is the most common indoor hazardous pollutant and has attracted great concern because its long-term exposure has adverse health effects on humans. Retention and catalytic oxidation of highly hazardous HCHO is an efficient and environmentally friendly method to use for air remediation, but a major obstacle to this procedure is the lack of an appropriate catalyst. Herein, two-dimensional magnetic C4N3 material with a 3d-transition metal as activate sites was systemically investigated in HCHO oxidation using density functional theory calculations. The results show that V-C4N3 and Cr-C4N3 have high structural stability and shallow activation barriers for O2 decomposition; these characteristics provide the necessary precursors for the subsequent oxidation reaction. Moreover, the V-C4N3 and Cr-C4N3 catalysts have unique selective adsorption and catalysis toward HCHO in a mixture of some typical in-door volatile organic compounds (VOCs) and air. The corresponding dynamic barrier for each reaction step was investigated and the mechanism involved in HCHO oxidation was revealed in detail. Aggregation of metal atoms in the V-C4N3 and Cr-C4N3 catalysts is prevented by enormous diffusion resistance, and this is further confirmed by AIMD simulations. These results provide insightful guidance for developing advanced magnetic catalysts for HCHO oxidation to improve the remediation of air contaminants.

Two-Dimensional Boron-Rich Monolayer BxN as High Capacity for Lithium-Ion Batteries: A First-Principles Study.

Owing to lightweight, abundant reserves, low cost, and nontoxicity, B-based two-dimensional (2D) materials, e.g., borophene, exhibit great potential as new anode materials with higher energy density for Li-ion batteries (LIBs). However, exfoliation of borophene from the Ag substrate remains the most daunting challenge due to their strong interfacial interactions, significantly restricting its practical applications. In this study, through first-principles swarm-intelligence structure calculations, we have found several Boron-rich boron nitride BxN materials (x = 2, 3, 4, and 5) with increased stability and weakened interactions with the Ag(111) substrate compared with δ6-borophene. A high cohesive energy and superior dynamical, thermodynamic, and mechanical stability provide strong feasibility for their experimental synthesis. The obtained BxN materials exhibit a high mechanical strength (94-226 N/m) and low interfacial bonding with the Ag substrate, from -0.043 to -0.054 eV Å-2, significantly smaller than that of δ6-borophene. Among them, B3N and B5N exhibit not only a remarkably high storage capacity of 1805-3153 mAh/g but also a low barrier energy and open-circuit voltage. Moreover, B2N showed a cross-sheet motion with a low barrier of 0.24 eV, which is unique compared with the in-plane diffusion in most other 2D electrode materials restricted by their quasi-flat geometry. BxN also exhibits excellent cyclability with improved metallic conductivity upon Li-ion intercalation, showing great potential in LIB applications. This study opens up a new avenue to explore B-rich 2D electrode materials in energy applications and provide instructive insights into borophene functionalization and exfoliation.

Adjusting the Covalency of Metal-Oxygen Bonds in LaCoO3 by Sr and Fe Cation Codoping to Achieve Highly Efficient Electrocatalysts for Aprotic Lithium-Oxygen Batteries.

Developing high-efficiency dual-functional catalysts to promote oxygen electrode reactions is critical for achieving high-performance aprotic lithium-oxygen (Li-O2) batteries. Herein, Sr and Fe cation-codoped LaCoO3 perovskite (La0.8Sr0.2Co0.8Fe0.2O3-σ, LSCFO) porous nanoparticles are fabricated as promising electrocatalysts for Li-O2 cells. The results demonstrate that the LSCFO-based Li-O2 batteries exhibit an extremely low overpotential of 0.32 V, ultrahigh specific capacity of 26 833 mA h g-1, and superior long-term cycling stability (200 cycles at 300 mA g-1). These prominent performances can be partially attributed to the existence of abundant coordination unsaturated sites caused by oxygen vacancies in LSCFO. Most importantly, density functional theory (DFT) calculations reveal that codoping of Sr and Fe cations in LaCoO3 results in the increased covalency of Co 3d-O 2p bonds and the transition of Co3+ from an ordinary low-spin state to an intermediate-spin state, eventually resulting in the transformation from nonconductor LCO to metallic LSCFO. In addition, based on the theoretical calculations, it is found that the inherent adsorption capability of LSCFO toward the LiO2 intermediate is reduced due to the increased covalency of Co 3d-O 2p bonds, leading to the formation of large granule-like Li2O2, which can be effectively decomposed on the LSCFO surface during the charging process. Notably, this work demonstrates a unique insight into the design of advanced perovskite oxide catalysts via adjusting the covalency of transition-metal-oxygen bonds for high-performance metal-air batteries.