Intercalant-induced V t2g orbital occupation in vanadium oxide cathode toward fast-charging aqueous zinc-ion batteries.

Intercalation-type layered oxides have been widely explored as cathode materials for aqueous zinc-ion batteries (ZIBs). Although high-rate capability has been achieved based on the pillar effect of various intercalants for widening interlayer space, an in-depth understanding of atomic orbital variations induced by intercalants is still unknown. Herein, we design an NH4+-intercalated vanadium oxide (NH4+-V2O5) for high-rate ZIBs, together with deeply investigating the role of the intercalant in terms of atomic orbital. Besides extended layer spacing, our X-ray spectroscopies reveal that the insertion of NH4+ could promote electron transition to 3dxy state of V t2g orbital in V2O5, which significantly accelerates the electron transfer and Zn-ion migration, further verified by DFT calculations. As results, the NH4+-V2O5 electrode delivers a high capacity of 430.0 mA h g-1 at 0.1 A g-1, especially excellent rate capability (101.0 mA h g-1 at 200 C), enabling fast charging within 18 s. Moreover, the reversible V t2g orbital and lattice space variation during cycling are found via ex-situ soft X-ray absorption spectrum and in-situ synchrotron radiation X-ray diffraction, respectively. This work provides an insight at orbital level in advanced cathode materials.

Analyzing the Active Site and Predicting the Overall Activity of Alloy Catalysts.

As one of the potential catalysts, disordered solid solution alloys can offer a wealth of catalytic sites. However, accurately evaluating their activity localization structure and overall activity from each individual site remains a formidable challenge. Herein, an approach based on density functional theory and machine learning was used to obtain a large number of sites of the Pt-Ru alloy as the model multisite catalyst for the hydrogen evolution reaction. Subsequently, a series of statistical approaches were employed to unveil the relationship between the geometric structure and overall activity. Based on the radial frequency distribution of metal elements and the distribution of ΔGH, we have identified the surface and subsurface sites occupied by Pt and Ru, respectively, as the most active sites. Particularly, the concept of equivalent site ratio predicts that the overall activity is highest when the Ru content is 20-30%. Furthermore, a series of Pt-Ru alloys were synthesized to validate the proposed theory. This provides crucial insights into understanding the origin of catalytic activity in alloys and thus will better guide the rational development of targeted multisite catalysts.

Universal Intercalation/Alloying Hybrid Mechanism with -ICOHP Criterion in MAX Toward Steadily Ascending Lithium-Ion Batteries.

Profiting from the unique atomic laminated structure, metallic conductivity, and superior mechanical properties, transition metal carbides and nitrides named MAX phases have shown great potential as anodes in lithium-ion batteries. However, the complexity of MAX configurations poses a challenge. To accelerate such application, a minus integrated crystal orbital Hamilton populations descriptor is innovatively proposed to rapidly evaluate the lithium storage potential of various MAX, along with density functional theory computations. It confirms that surface A-element atoms bound to lithium ions have odds of escaping from MAX. Interestingly, the activated A-element atoms enhance the reversible uptake of lithium ions by MAX anodes through an efficient alloying reaction. As an experimental verification, the charge compensation and SnxLiy phase evolution of designed Zr2SnC MAX with optimized structure is visualized via in situ synchrotron radiation XRD and XAFS technique, which further clarifies the theoretically expected intercalation/alloying hybrid storage mechanism. Notably, Zr2SnC electrodes achieve remarkably 219.8% negative capacity attenuation over 3200 cycles at 1 A g-1. In principle, this work provides a reference for the design and development of advanced MAX electrodes, which is essential to explore diversified applications of the MAX family in specific energy fields.

X-ray Insights into Formation of -O Functional Groups on MXenes: Two-Step Dehydrogenation of Adsorbed Water.

Engineered MXene surfaces with more -O functional groups are feasible for realizing higher energy density due to their higher theoretical capacitance. However, there have been only a few explorations of this regulation mechanism. Investigating the formation source and mechanism is conducive to expanding the adjustment method from the top-down perspective. Herein, for the first time, the formation dynamics of -O functional groups on Mo2CTx are discovered as a two-step dehydrogenation of adsorbed water through in situ near-ambient-pressure X-ray photoelectron spectroscopy, further confirmed by ab initio molecular dynamics simulations. From this, the controllable substitution of -F functional groups with -O functional groups is achieved on Mo2CTx during electrochemical cycling in an aqueous electrolyte. The obtained Mo2CTx with rich -O groups exhibits a high capacitance of 163.2 F g -1 at 50 mV s -1, together with excellent stability. These results offer new insights toward engineering surface functional groups of MXenes for many specific applications.

Operando Exploring and Modulating Phase Evolution Chemistry from MAX to MXenes in Molten Salt Synthesis.

Lewis acidic molten salt method is a promising synthesis strategy for achieving MXenes with controllable surface termination from numerous MAX materials. Understanding the phase evolution chemistry during etching and post-processing is highly desirable but remains a key challenge due to the lack of suitable in-situ characterizations and the complexity of the reaction process. Herein, we introduce an operando synchrotron radiation X-ray diffraction (SRXRD) technique to unveil the phase evolution process of Nb2GaC MAX under a molten-salt ambient, proposing a controllable synthesis to achieve optimal etching through precise temperature and time adjustment. Subsequently, the phase structure of Nb2CTx MXenes is successfully tailored from hexagonal to amorphous by time-dependent persulfate oxidation. The resulting amorphous Nb2CTx with a well-patterned morphology and numerous chloride terminations exhibits highly improved specific capacity, rate capability, and long cycling for Li+ storage with a Cl-containing surface protective film. Addressing the time-related phase evolution during the entire molten salt strategy provides new insights into achieving higher efficiency and controllability in preparing MXenes and shows great potential in high-performance energy storage systems based on MXenes.

[Parkinson's disease diagnosis based on local statistics of speech signal in time-frequency domain].

For speech detection in Parkinson's patients, we proposed a method based on time-frequency domain gradient statistics to analyze speech disorders of Parkinson's patients. In this method, speech signal was first converted to time-frequency domain (time-frequency representation). In the process, the speech signal was divided into frames. Through calculation, each frame was Fourier transformed to obtain the energy spectrum, which was mapped to the image space for visualization. Secondly, deviations values of each energy data on time axis and frequency axis was counted. According to deviations values, the gradient statistical features were used to show the abrupt changes of energy value in different time-domains and frequency-domains. Finally, KNN classifier was applied to classify the extracted gradient statistical features. In this paper, experiments on different speech datasets of Parkinson's patients showed that the gradient statistical features extracted in this paper had stronger clustering in classification. Compared with the classification results based on traditional features and deep learning features, the gradient statistical features extracted in this paper were better in classification accuracy, specificity and sensitivity. The experimental results show that the gradient statistical features proposed in this paper are feasible in speech classification diagnosis of Parkinson's patients.

Ultrasmall Co3O4 nanoparticles as a long-lived high-rate lithium-ion battery anode.

Herein, ultrasmall nanostructured Co3O4 particles have been prepared by a facile two-step synthetic method and furthermore applied to lithium-ion batteries. Benefitting from an increased specific surface area and improved tolerance for volume expansion, they deliver an extremely high specific capacity of 1432.7 mA h g-1 at 0.1 A g-1 and an outstandingly long cycle life with about 511.2 mA h g-1 at 10 A g-1 after 2000 cycles. This work will pave a new way to engineer advanced electrode materials for long-lived high-rate lithium-ion batteries.

Intrinsic room-temperature ferromagnetism in a two-dimensional semiconducting metal-organic framework.

The development of two-dimensional (2D) magnetic semiconductors with room-temperature ferromagnetism is a significant challenge in materials science and is important for the development of next-generation spintronic devices. Herein, we demonstrate that a 2D semiconducting antiferromagnetic Cu-MOF can be endowed with intrinsic room-temperature ferromagnetic coupling using a ligand cleavage strategy to regulate the inner magnetic interaction within the Cu dimers. Using the element-selective X-ray magnetic circular dichroism (XMCD) technique, we provide unambiguous evidence for intrinsic ferromagnetism. Exhaustive structural characterizations confirm that the change of magnetic coupling is caused by the increased distance between Cu atoms within a Cu dimer. Theoretical calculations reveal that the ferromagnetic coupling is enhanced with the increased Cu-Cu distance, which depresses the hybridization between 3d orbitals of nearest Cu atoms. Our work provides an effective avenue to design and fabricate MOF-based semiconducting room-temperature ferromagnetic materials and promotes their practical applications in next-generation spintronic devices.

Anion Additive Integrated Electric Double Layer and Solvation Shell for Aqueous Zinc Ion Battery.

Aqueous zinc ion batteries (AZIBs) show great potential in large-scale energy storage systems. However, the inferior cycling life due to water-induced parasitic reactions and uncontrollable dendrites growth impede their application. Electrolyte optimization via the use of additives is a promising strategy to enhance the stability of AZIBs. Nevertheless, the mechanism of optimal multifunctional additive strategy requires further exploration. Herein, sodium dodecyl benzene sulfonate (SDBS) is proposed as a dual-functional additive in ZnSO4 electrolyte. Benefiting from the additive, both side reactions and zinc dendrites growth are significantly inhibited. Further, a synchrotron radiational spectroscopic study is employed to investigate SDB- adjusted electric double layer (EDL) near the Zn surface and the optimized solvation sheath of Zn2+ . First-principles calculations verify the firm adsorption of SDB- , and restriction of random diffusion of Zn2+ on the Zn surface. In particular, the SDBS additive endows Zn||Zn symmetric cells with a 1035 h ultra-stable plating/stripping at 0.2 mA cm-2 . This work not only provides a promising design strategy by dual-functional electrolyte additives for high stable AZIBs, but also exhibits the prospect of synchrotron radiation spectroscopy analysis on surface EDL and Zn2+ solvation shell optimization.

Monolayer Thiol Engineered Covalent Interface toward Stable Zinc Metal Anode.

Interface engineering of zinc metal anodes is a promising remedy to relieve their inferior stability caused by dendrite growth and side reactions. Nevertheless, the low affinity and additional weight of the protective coating remain obstacles to their further implementation. Here, aroused by DFT simulation, self-assembled monolayers (SAMs) are selectively constructed to enhance the stability of zinc metal anodes in dilute aqueous electrolytes. It is found that the monolayer thiol molecules relatively prefer to selectively graft onto the unstable zinc crystal facets through strong Zn-S chemical interactions to engineer a covalent interface, enabling the uniform deposition of Zn2+ onto (002) crystal facets. Therefore, dendrite-free anodes with suppressed side reactions can be achieved, proven by in situ optical visualization and differential electrochemical mass spectrometry (DEMS). In particular, the thiol endows the symmetric cells with a 4000 h ultrastable plating/stripping at a specific current density of 1.0 mA cm-2, much superior to those of bare zinc anodes. Additionally, the full battery of modified anodes enables stable cycling of 87.2% capacity retention after 3300 cycles. By selectively capping unstable crystal facets with inert molecules, this work provides a promising design strategy at the molecular level for stable metal anodes.

3D V2CTx-rGO Architectures with Optimized Ion Transport Channels toward Fast Lithium-Ion Storage.

Two-dimensional (2D) MXene materials show great potential in energy storage devices. However, the self-restacking of MXene nanosheets and the sluggish lithium-ion (Li+) kinetics greatly hinder their rate capability and cycling stability. Herein, we interlink 2D V2CTx MXene nanosheets with rGO to construct a 3D porous V2CTx-rGO composite. X-ray spectroscopy study reveals the close interfacial contact between V2CTx and rGO via electron transfer from V to C atoms. Benefiting from the close combination and optimized ion transport channel, V2CTx-rGO offers a high-rate Li+ storage performance and excellent cycling stability over 2000 cycles with negligible capacity attenuation. Moreover, it exhibits a dominant mechanism of intercalation pseudocapacitance and efficient Li+ transport proved by density functional theory calculation. This rationally designed 3D V2CTx-rGO has implications for the study of the MXene composite's structure and energy storage devices with high rate and stability.

Defect engineering on V2O3 cathode for long-cycling aqueous zinc metal batteries.

Defect engineering is a strategy that is attracting widespread attention for the possibility of modifying battery active materials in order to improve the cycling stability of the electrodes. However, accurate investigation and quantification of the effect of the defects on the electrochemical energy storage performance of the cell are not trivial tasks. Herein, we report the quantification of vanadium-defective clusters (i.e., up to 5.7%) in the V2O3 lattice via neutron and X-ray powder diffraction measurements, positron annihilation lifetime spectroscopy, and synchrotron-based X-ray analysis. When the vanadium-defective V2O3 is employed as cathode active material in an aqueous Zn coin cell configuration, capacity retention of about 81% after 30,000 cycles at 5 A g-1 is achieved. Density functional theory calculations indicate that the vanadium-defective clusters can provide favorable sites for reversible Zn-ion storage. Moreover, the vanadium-defective clusters allow the storage of Zn ions in V2O3, which reduces the electrostatic interaction between the host material and the multivalent ions.

The Two-Sided Effect of Leader Unethical Pro-organizational Behaviors on Subordinates' Behaviors: A Mediated Moderation Model.

Research suggests that unethical pro-organizational behavior (UPB) has two conflicting characteristics: unethical and pro-organizational. However, little attention has been paid to the negative and positive outcomes of UPB. Therefore, the present study aimed to fill this gap by examining a mediated moderation model on the effects of leader UPB on their subordinates' behaviors. Based on social information processing theory and three-wave survey data from 204 supervisor-subordinate dyads in China, we found that the mixed relationships between leader UPB and subordinates' behaviors were dependent on the leader's Machiavellianism. Specifically, for high Machiavellian leaders, their UPB was positively related to subordinates' unethical behaviors via subordinates' moral disengagement. For low Machiavellian leaders, their UPB was positively related to subordinates' organizational citizenship behaviors via their organizational identification. The theoretical contributions and practical implications of the findings are discussed.

Design of Muscle Reflex Control for Upright Standing Push-Recovery Based on a Series Elastic Robot Ankle Joint.

In physical human-robot interaction environment, ankle joint muscle reflex control remains significant and promising in human bipedal stance. The reflex control mechanism contains rich information of human joint dynamic behavior, which is valuable in the application of real-time decoding motion intention. Thus, investigating the human muscle reflex mechanism is not only meaningful in human physiology study but also useful for the robotic system design in the field of human-robot physical interaction. In this paper, a specialized ankle joint muscle reflex control algorithm for human upright standing push-recovery is proposed. The proposed control algorithm is composed of a proportional-derivative (PD)-like controller and a positive force controller, which are employed to mimic the human muscle stretch reflex and muscle tendon force reflex, respectively. Reflex gains are regulated by muscle activation levels of contralateral ankle muscles. The proposed method was implemented on a self-designed series elastic robot ankle joint (SERAJ), where the series elastic actuator (SEA) has the potential to mimic human muscle-tendon unit (MTU). During the push-recovery experimental study, the surface electromyography (sEMG), ankle torque, body sway angle, and velocity of each subject were recorded in the case where the SERAJ was unilaterally kneed on each subject. The experimental results indicate that the proposed muscle reflex control method can easily realize upright standing push-recovery behavior, which is analogous to the original human behavior.