Electrochemically Intercalated Ti3C2 MXene Bulk for Expanding Interlayer Spacing and Enhancing Supercapacitor Performance.

Tuning the interlayer spacing of 2D MXenes bulk mainly focuses on hydrothermal intercalation, physiotherapy intercalation, and ion exchange intercalation. Nevertheless, the feasibility of electrochemical intercalation technology for expanding the interlayer spacing of Ti3C2 MXene bulk is not yet clear, and further research is required to advance it. Here, we employed an electrochemical intercalation technology to successfully embed metal cations (K+ and Na+) into the interlayer structure of Ti3C2 MXene bulk, expanding the interlayer spacing from ∼10.50 to ∼13.10 Šby K+ intercalation, which can broaden electron/ion transport channels and enhance supercapacitor performance. Compared to the pristine Ti3C2 MXene bulk, the specific capacitance value increased by a factor of 2.8. Moreover, the intercalated MXene also exhibits excellent rate capability, with an increase from 47.32 to 70.20%. This work opens up a new path for the modification of Ti3C2 MXene bulk.

Ca/Li Synergetic-Doped Na0.67Ni0.33Mn0.67O2 to Realize P2-O2 Phase Transition Suppression for High-Performance Sodium-Ion Batteries.

P2-type layered transition metal oxide Na0.67Ni0.33Mn0.67O2 is considered as a promising cathode for advanced sodium-ion batteries due to its high theoretical specific capacity. However, the P2-type cathode suffers severe P2-O2 phase transition during cycling process, resulting unsatisfactory cyclic stability and rate capability. Herein, a Ca/Li co-doped P2-type Na0.62Ca0.05Ni0.33Mn0.57Li0.10O2 (NCNMLO) cathode material was synthesized through a simple sol-gel method. With the synergistic effect of Ca-doping at Na sites and Li substitution at transition metal (TM) sites, the cathode achieves an excellent electrochemical performance due to the inhibited P2-O2 phase transition and improved ion diffusion with Na+/vacancy disordering arrangement. The NCNMLO cathode exhibits a good cyclic stability with 70.8% of capacity retention at 1 C after 200 cycles and excellent rate capability with 40.1 mAh g-1 at 20 C. The dual sites doping strategy provides an effective and simple approach for designing high-performance layered oxide cathode materials for sodium-ion batteries.

Amino Group-Aided Efficient Regeneration Targeting Structural Defects and Inactive FePO4 Phase for Degraded LiFePO4 Cathodes.

It is urgent to develop efficient recycling methods for spent LiFePO4 cathodes to cope with the upcoming peak of power battery retirement. Compared with the traditional metallurgical recovery methods that lack satisfactory economic and environmental benefits, the direct regeneration seems to be a promising option at present. However, a simple direct lithium replenishment cannot effectively repair and regenerate the cathodes due to the serious structural damage of the spent LiFePO4. Herein, the spent LiFePO4 cathodes are directly regenerated by a thiourea-assisted solid-phase sintering process. The density functional theory calculation indicates that thiourea has a targeted repair effect on the antisite defects and inactive FePO4 phase in the spent cathode due to the associative priority of amino group (─NH2) in thiourea with Fe ions: Fe3+─N > Fe2+─N. Meanwhile, the pyrolysis products of thiourea can also create an optimal reducing atmosphere and inhibit the agglomeration of particles in the high temperature restoration process. The regenerated LiFePO4 exhibits an excellent electrochemical performance, which is comparable to that of commercial LiFePO4. This targeted restoration has improved the efficiency of direct regeneration, which is expected to achieve large-scale recycling of spent LiFePO4.

Linear-Organic-Ions In Situ-Intercalated MoS2 for Unveiling Capacitive Energy Storage Relies on the Chain Length.

Intercalating linear-organic-ions into the MoS2 interlayer is beneficial for optimizing electrons/ions' capacitive storage behavior. The chain length, as an important parameter of linear organic ions, can lead to differences in the dispersion, polarity, critical micelle concentration of organic ions, and steric hindrance to the growth of MoS2 nanosheets. Up until now, the relationship between chain length, synthesis of intercalated-MoS2, and capacitive energy storage has not been unveiled. Herein, we have designed an in situ-intercalation route that is simple, efficient, and high yield for inserting four types of linear organic ions into the interlayer of MoS2 to synthesize four types of in situ-intercalated MoS2 samples. After organic-ion intercalation, the expanded interlayer spacing achieved the introduction of intercalation-type pseudocapacitors, as confirmed by ex situ XRD. Improved extra capacitance is verified due to the enlarged ion storage space from a synergistic spatial effect in the broken-shell-hollow ball. Additionally, the generation of high-valent Mo (+5 and +6) and S-vacancies is beneficial for energy storage. More importantly, according to density functional theory (DFT) calculations, as the chain length increases, the number of negative adsorption sites and the total adsorption ability also increase, leading to significantly improved specific capacitance. This work will provide an archetype for the preparation of in situ-intercalated layered materials and unveil capacitive energy storage that relies on the organic-ion chain length.

Balancing Polarization and Breakdown for High Capacitive Energy Storage by Microstructure Design.

The compromise of contradictive parameters, polarization, and breakdown strength, is necessary to achieve a high energy storage performance. The two can be tuned, regardless of material types, by controlling microstructures: amorphous states possess higher breakdown strength, while crystalline states have larger polarization. However, how to achieve a balance of amorphous and crystalline phases requires systematic and quantitative investigations. Herein, the trade-off between polarization and breakdown field is comprehensively evaluated with the evolution of microstructure, i.e., grain size and crystallinity, by phase-field simulations. The results indicate small grain size (≈10-35 nm) with moderate crystallinity (≈60-80%) is more beneficial to maintain relatively high polarization and breakdown field simultaneously, consequently contributing to a high overall energy storage performance. Experimentally, therefore an ultrahigh energy density of 131 J cm-3 is achieved with a high efficiency of 81.6% in the microcrystal-amorphous dual-phase Bi3NdTi4O12 films. This work provides a guidance to substantially enhance dielectric energy storage by a simple and effective microstructure design.

Recent progress in critical electrode and electrolyte materials for flexible zinc-ion batteries.

With the increasing popularity of flexible and wearable electronic devices, the demand for power supplies that can be easily bent or worn is also rapidly growing. However, traditional lithium ion batteries are difficult to adapt to complex wearable devices because of their unsatisfactory flexibility and thickness as well as safety issues. Zinc-ion batteries have several advantages, including low redox potential, high theoretical capacity, high safety, and abundant reserves. These features make flexible zinc-ion batteries (FZIBs) an ideal wearable energy storage device candidate. The electrochemical performance and mechanical deformability of FZIBs were pivotally determined based on the properties of their electrode and electrolyte. Herein, we summarize some recent advances from 2015 to 2023 in the design and preparation of various electrode and electrolyte materials for FZIBs with controllable morphology and structure, excellent mechanical property, and enhanced electrochemical performance. Moreover, efforts to explore the potential practical applications of FZIBs have also been considered. Finally, we present and discuss current challenges and opportunities for the development of high-performance FZIBs.

Two Birds with One Stone: V4 C3 MXene Synergistically Promoted VS2 Cathode and Zinc Anode for High-Performance Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are considered to be a rising star in the large-scale energy storage area because of their low cost and environmental friendliness properties. However, the limited electrochemical performance of the cathode and severe zinc dendrite of the anode severely hinder the practical application of AZIBs. Herein, a novel 3D interconnected VS2 ⊥V4 C3 Tx heterostructure material is prepared via one-step solvothermal method. Morphological and structural characterizations show that VS2 nanosheets are uniformly and dispersedly distributed on the surface of the V4 C3 MXene substrate, which can effectively suppress volume change of the VS2 . Owing to the open heterostructure along with the high conductivity of V4 C3 MXene, the VS2 ⊥V4 C3 Tx cathode shows a high specific capacity of 273.9 mAh g-1 at 1 A g-1 and an excellent rate capability of 143.2 mAh g-1 at 20 A g-1 . The V4 C3 MXene can also effectively suppress zinc dendrite growth when used as protective layer for the Zn anode, making the V4 C3 Tx @Zn symmetric cell with a stable voltage profile for ≈1700 h. Benefitting from the synergistic modification effect of V4 C3 MXene on both the cathode and anode, the VS2 ⊥V4 C3 Tx ||V4 C3 Tx @Zn battery exhibits a long cycling lifespan of 5000 cycles with a capacity of 157.1 mAh g-1 at 5A g-1 .

Surface Modification Driven Initial Coulombic Efficiency and Rate Performance Enhancement of Li1.2 Mn0.54 Ni0.13 Co0.13 O2 Cathode.

Due to its high energy density and low cost, Li-rich Mn-based layered oxides are considered potential cathode materials for next generation Li-ion batteries. However, they still suffer from the serious obstacle of low initial Coulombic efficiency, which is detrimental to their practical application. Here, an efficient surface modification method via NH4 H2 PO4 assisted pyrolysis is performed to improve the Coulombic efficiency of Li1.2 Mn0.54 Ni0.13 Co0.13 O2 , where appropriate oxygen vacancies, Li3 PO4 and spinel phase are synchronously generated in the surface layer of LMR microspheres. Under the synergistic effect of the oxygen vacancies and spinel phase, the unavoidable oxygen release in the cycling process was effectively suppressed. Moreover, the induced Li3 PO4 nanolayer could boost the lithium-ion diffusion and mitigate the dissolution of transition metal ions, especially manganese ions, in the material. The optimally modified sample yielded an impressive initial Coulombic efficiency and outstanding rate performance.

Regulation of Sulfur Atoms in MoSx by Magneto-Electrodeposition for Hydrogen Evolution Reaction.

Compared with crystalline molybdenum sulfide (MoS2 ) employed as an efficient hydrogen evolution reaction (HER) catalyst, amorphous MoSx exhibits better activity. To synthesize amorphous MoSx , electrodeposition serving as a convenient and time-saving method is successfully applied. However, the loading mass is hindered by limited mass transfer efficiency and the available active sites require further improvement. Herein, magneto-electrodeposition is developed to synthesize MoSx with magnetic fields up to 9 T to investigate the effects of a magnetic field in the electrodeposition processing, as well as the induced electrochemical performance. Owing to the magneto-hydrodynamic effect, the loading mass of MoSx is obviously increased, and the terminal S2- serving as the active site is enhanced. The optimized MoSx catalyst delivers outstanding HER performance, achieving an overpotential of 50 mV at a current density of 10 mA cm-2 and the corresponding Tafel slope of 59 mV dec-1 . The introduction of a magnetic field during the electrodeposition process will provide a novel route to prepare amorphous MoSx with improved electrochemical performance.

Phase Engineering of W-Doped MoS2 by Magneto-Hydrothermal Synthesis for Hydrogen Evolution Reaction.

Molybdenum disulfide (MoS2 ) has been proved as an excellent potential hydrogen evolution reaction (HER) catalyst. Compared with thermodynamically stable 2H-MoS2 , 1T-MoS2 exhibits higher conductivity and catalytic activity, whereas it is usually difficult to prepare since of thermodynamically metastable. Herein, a feasible method is reported to fabricate ambient-stable MoS2 with high concentration 1T phase through magnetic free energy synergistic microstrain induced by W doping under low magnetic field. The 1T phase proportion in MoS2 can be as high as 80% and is ambient-stable for more than one year. The catalyst prepared under a magnetic field of 3 T delivers an overpotential of 195 mV at a current density of 10 mA cm-2 and has a long-term stability over 50 h. This work provides a novel strategy for preparation of MoS2 with high 1T concentration and high stability.

Defect-Free Few-Layer M4 C3 Tx (M = V, Nb, Ta) MXene Nanosheets: Synthesis, Characterization, and Physicochemical Properties.

High-quality few-layer M4 C3 Tx (M = V, Nb, Ta) MXenes are very important for applications and are necessary for clarifying their physicochemical properties. However, the difficulty in etching for themselves and the existence of MC/MC1-δ and M-Al alloy impurities in their M4 AlC3 precursors seriously hinder the achievement of defect-free few-layer M4 C3 Tx (M = V, Nb, Ta) MXenes nanosheets. Herein, three different defect-free few-layer M4 C3 Tx (M = V, Nb, Ta) nanosheets are obtained by using a universal synthesis strategy of calcination, selective etching, intercalation, and exfoliation. Comprehensive characterizations confirm their defect-free few-layer structure feature, large interlayer spacing (1.702-1.955 nm), types of functional groups (-OH, -F, -O), and abundant valance states (M5+ , M4+ , M3+ , M2+ , M0 ). M4 C3 Tx (M = V, Nb, Ta) free-standing films obtained by vacuum filtration of few-layer M4 C3 Tx inks show good hydrophilia, high thermostability, and conductivity. A roadmap on synthesis of defect-free few-layer M4 C3 Tx (M = V, Nb, Ta) nanosheets are proposed and three key points are summarized. This work provides detailed guidelines for the synthesis of other defect-free few-layer MXenes nanosheets, but also will stimulate extensive functional explorations for M4 C3 Tx (M = V, Nb, Ta) MXenes nanosheets in the future.

Synthesis of porous LaNiO3 thin films by chemical solution deposition for enhanced oxygen evolution reaction.

Herein, a facile chemical solution deposition (CSD) strategy is adopted to synthesize LaNiO3 (LNO) thin films with an obvious porous structure (P-LNO). It is demonstrated that the porous structure can greatly promote the OER performance of LNO, requiring an overpotential of 367 mV to achieve 10 mA cm-2, which is much lower than that of a normal LNO thin film (478 mV). As revealed by the following experimental results, the presence of the porous structure offers more exposed active sites and promotes electron transfer between catalysts and electrolyte, giving rise to an enhanced OER performance of the P-LNO film.

Magneto-electrochemistry driven ultralong-life Zn-VS2 aqueous zinc-ion batteries.

The development of high energy density and long cycle lifespan aqueous zinc ion batteries is hindered by the limited cathode materials and serious zinc dendrite growth. In this work, a defect-rich VS2 cathode material is manufactured by in situ electrochemical defect engineering under high charge cut-off voltage. Owing to the rich abundant vacancies and lattice distortion in the ab plane, the tailored VS2 can unlock the transport path of Zn2+ along the c-axis, enabling 3D Zn2+ transport along both the ab plane and c-axis, and reduce the electrostatic interaction between VS2 and zinc ions, thus achieving excellent rate capability (332 mA h g-1 and 227.8 mA h g-1 at 1 A g-1 and 20 A g-1, respectively). The thermally favorable intercalation and 3D rapid transport of Zn2+ in the defect-rich VS2 are verified by multiple ex situ characterizations and density functional theory (DFT) calculations. However, the long cycling stability of the Zn-VS2 battery is still unsatisfactory due to the Zn dendrite issue. It can be found that the introduction of an external magnetic field enables changing the movement of Zn2+, suppressing the growth of zinc dendrites, and resulting in enhanced cycling stability from about 90 to 600 h in the Zn||Zn symmetric cell. As a result, a high-performance Zn-VS2 full cell is realized by operating under a weak magnetic field, which shows an ultralong cycle lifespan with a capacity of 126 mA h g-1 after 7400 cycles at 5 A g-1, and delivers the highest energy density of 304.7 W h kg-1 and maximum power density of 17.8 kW kg-1.

Carbon Foam-Supported VS2 Cathode for High-Performance Flexible Self-Healing Quasi-Solid-State Zinc-Ion Batteries.

As the new generation of energy storage systems, the flexible battery can effectively broaden the application area and scope of energy storage devices. Flexibility and energy density are the two core evaluation parameters for the flexible battery. In this work, a flexible VS2 material (VS2 @CF) is fabricated by growing the VS2 nanosheet arrays on carbon foam (CF) using a simple hydrothermal method. Benefiting from the high electric conductivity and 3D foam structure, VS2 @CF shows an excellent rate capability (172.8 mAh g-1 at 5 A g-1 ) and cycling performance (130.2 mAh g-1 at 1 A g-1 after 1000 cycles) when it served as cathode material for aqueous zinc-ion batteries. More importantly, the quasi-solid-state battery VS2 @CF//Zn@CF assembled by the VS2 @CF cathode, CF-supported Zn anode, and a self-healing gel electrolyte also exhibits excellent rate capability (261.5 and 149.8 mAh g-1 at 0.2 and 5 A g-1 , respectively) and cycle performance with a capacity of 126.6 mAh g-1 after 100 cycles at 1 A g-1 . Moreover, the VS2 @CF//Zn@CF full cell also shows good flexible and self-healing properties, which can be charged and discharged normally under different bending angles and after being destroyed and then self-healing.

Crystallinity Tuning of Na3 V2 (PO4 )3 : Unlocking Sodium Storage Capacity and Inducing Pseudocapacitance Behavior.

As a promising cathode material of sodium-ion batteries, Na3 V2 (PO4 )3 (NVP) has attracted extensive attention in recent years due to its high stability and fast Na+ ion diffusion. However, the reversible capacity based on the two-electron reaction mechanism is not satisfactory limited by the inactive M1 lattice sites during the insertion/extraction process. Herein, self-supporting 3D porous NVP materials with different crystallinity are fabricated on carbon foam substrates by a facile electrostatic spray deposition method. The V5+ /V4+ redox couple is effectively activated and the three-electron reactions are realized in NVP for sodium storage by a proper crystallinity tuning. In a disordered NVP sample, an ultra-high specific capacity of 179.6 mAh g-1 at 0.2 C is achieved due to the coexistence of redox reactions of the V4+ /V3+ and V5+ /V4+ couples. Moreover, a pseudocapacitive charge storage mechanism induced by the disordered structure is first observed in the NVP electrode. An innovative model is given to understand the disorder-induced-pseudocapacitance phenomenon in this polyanion cathode material.

Quenching and Electrical Current Poling Effect on Improved Ferroelectric and Piezoelectric Properties in BiFeO3-Based High-Temperature Piezoceramics.

The effects of quenching on the structural, electrical, dielectric, ferroelectric (FE), and piezoelectric properties are investigated systematically in the 0.85BiFe1-xCrxO3-0.15BaTi1-xMnxO3 (0 ≤ x ≤ 0.03) ceramics. Optimal piezoelectricity and FE Curie temperature are obtained through optimized quenching rate and temperature. Quenching effect on piezoelectricity is especially significant for the samples near morphotropic phase boundaries (MPB), which can be ascribed to quenching-induced changes in phase ratio (rhombohedral and tetragonal phase) and domain structure/defect dipole orientation. Moreover, a new poling method, that is, cooling the sample at a constant dc current across FE TC, is established to improve the piezoelectricity. This work not only reveals the possible mechanism of quenching effect on the improved piezoelectricity in the BFO-based piezoceramics (especially near the MPB) but also suggests an electric current poling strategy for improving piezoelectricity by suppressing the defect dipole effects in BFO-based and even other piezoelectrics.

Intercalation Reaction in Amorphous Layer-Wrapped Ni0.2Mo0.8N/Ni3N Heterostructure Toward Efficient Lithium-Ion Storage.

Transition metal nitrides (TMNs) with high specific capacity and electric conductivity have drawn considerable attention as electrode materials of lithium-ion batteries (LIBs). However, the cycling stability of most TMNs is not satisfactory, which was caused by the large volume variation during cycles due to their intrinsic conversion reaction mechanism. Herein, by rational design, a much stable tremella-like Ni0.2Mo0.8N/Ni3N heterostructure with amorphous Ni0.2Mo0.8N wrapped layer has been fabricated. The Ni3N particles worked as pillars to support the Ni0.2Mo0.8N material as well as conductive medium to facilitate ionic and electronic transport. The amorphous layer can relieve the structural stress of Ni0.2Mo0.8N during cycles. Moreover, an exotic intercalation-type reaction mechanism in the ternary nitride Ni0.2Mo0.8N was revealed by a series ex situ and in situ characterization. Profiting from these advantages, the Ni0.2Mo0.8N/Ni3N heterostructure anode displays an outstanding electrochemical performance with a high initial reversible discharge capacity of 1001.6 mA h g-1 at 0.1 A g-1, excellent cycle stability of 695.5 mA h g-1 at 2 A g-1 after 600 cycles, and superior rate capability of 595.3 mA h g-1 at a high current density of 5 A g-1. This work provides a new insight for designing high efficiency LIBs based on intercalation reaction for practical applications.

Colossal 3D Electrical Anisotropy of MoAlB Single Crystal.

3D anisotropic functional properties (such as magnetic, electrical, thermal, and optical properties, etc.) in a single material are not only beneficial to the multipurpose of a material, but also helpful to enrich the regulatory dimensionality of functional materials. Herein, a colossal 3D electrical anisotropy of layered MAB-phase MoAlB single crystal is introduced and dissected. Using high-temperature metal-solution method, high-quality MoAlB single crystals are obtained and a surprisingly strong out-of-plane (σa /σb  = 1.43 × 105 , at 2 K) and in-plane (σa /σc  = 12.12, at 2 K) electrical anisotropies are first observed. After a series of experimental and theoretical investigations, it is demonstrated that the 3D anisotropic crystal structure and chemical bond of MoAlB result in its 3D anisotropic phonon vibration and electronic structure, influence the corresponding electron-electron as well as electron-phonon interactions, and finally give rise to its colossal 3D anisotropy of electrical conductivity. This work experimentally and theoretically proves MoAlB single crystal possessing the 3D anisotropies of crystal structure, chemical bond, phonon vibration, electronic structure, and electrical transport, but also provides a promising platform for the future design of functionalized electronic devices as well as synthesis of new and large-sized in-plane anisotropic 2D material (MoBene).

Magneto-Electrodeposition of 3D Cross-Linked NiCo-LDH for Flexible High-Performance Supercapacitors.

Layered double hydroxides (LDHs) with outstanding redox activity on flexible current collectors can serve as ideal cathode materials for flexible hybrid supercapacitors in wearable energy storage devices. Electrodeposition is a facile, time-saving, and economical technique to fabricate LDHs. The limited loading mass induced by insufficient mass transport and finite exposure of active sites, however, greatly hinders the improvement of areal capacity. Herein, magneto-electrodeposition (MED) under high magnetic fields up to 9 T is developed to fabricate NiCo-LDH on flexible carbon cloth (CC) as well as Ti3 C2 Tx functionalized CC. Owing to the magneto-hydrodynamic effect induced by magnetic-electric field coupling, the loading mass and exposure of active sites are significantly increased. Moreover, a 3D cross-linked nest-like microstructure is constructed. The MED-derived NiCo-LDH delivers an ultrahigh areal capacity of 3.12 C cm-2 at 1 mA cm-2 and as-fabricated flexible hybrid supercapacitors show an excellent energy density with an outstanding cycling stability. This work provides a novel route to improve electrochemical performances of layered materials through MED technique.

Pressure-Induced Electronic and Structural Transition in Nodal-Line Semimetal ZrSiSe.

The nodal-line semimetals have recently gained attention as a promising material due to their exotic electronic structure and properties. Here, we investigated the structural evolution and physical properties of nodal-line semimetal ZrSiSe under pressure via experiments and theoretical calculations. An isostructural electronic transition is observed at ∼6 GPa. Upon further compression, the original tetragonal phase starts to transform into an orthorhombic phase at ∼13 GPa and the two phases coexist until the maximal experimental pressure. By analysis of the electronic band structure, we suggest that the significant changes in the Fermi surface contribute to the occurrence of the isostructural electronic transition. The results provide a new insight into the structure and properties of ZrSiSe.