Enhancing Reversibility and Kinetics of Anionic Redox in O3-NaLi1/3Mn2/3O2 through Controlled P2 Intergrowth.

Anionic redox chemistry can surpass theoretical limits of conventional layered oxide cathodes in energy density. A recent model system of sodium-ion batteries, O3-NaLi1/3Mn2/3O2, demonstrated full anionic redox capacity but is limited in reversibility and kinetics due to irreversible structural rearrangement and oxygen loss. Solutions to these issues are missing due to the challenging synthesis. Here, we harness the unique structural richness of sodium layered oxides and realize a controlled ratio of P2 structural intergrowth in this model compound with the overall composition maintained. The resulted O3 with 27% P2 intergrowth structure delivers an excellent initial Coulombic efficiency of 87%, comparable to the state-of-the-art Li-rich NMCs. This improvement is attributed to the effective suppression of irreversible oxygen release and structural changes, evidenced by operando Differential Electrochemical Mass Spectroscopy and X-ray Diffraction. The as-prepared intergrowth material, based on the environmentally benign Mn, exhibits a reversible capacity of 226 mAh g-1 at C/20 rate with excellent cycling stability stemming from the redox reactions of oxygen and manganese. Our work isolates the role of P2 structural intergrowth and thereby introduces a novel strategy to enhance the reversibility and kinetics of anionic redox reactions in sodium layered cathodes without compromising capacity.

Enhanced polarization switching characteristics of HfO2 ultrathin films via acceptor-donor co-doping.

In the realm of ferroelectric memories, HfO2-based ferroelectrics stand out because of their exceptional CMOS compatibility and scalability. Nevertheless, their switchable polarization and switching speed are not on par with those of perovskite ferroelectrics. It is widely acknowledged that defects play a crucial role in stabilizing the metastable polar phase of HfO2. Simultaneously, defects also pin the domain walls and impede the switching process, ultimately rendering the sluggish switching of HfO2. Herein, we present an effective strategy involving acceptor-donor co-doping to effectively tackle this dilemma. Remarkably enhanced ferroelectricity and the fastest switching process ever reported among HfO2 polar devices are observed in La3+-Ta5+ co-doped HfO2 ultrathin films. Moreover, robust macro-electrical characteristics of co-doped films persist even at a thickness as low as 3 nm, expanding potential applications of HfO2 in ultrathin devices. Our systematic investigations further demonstrate that synergistic effects of uniform microstructure and smaller switching barrier introduced by co-doping ensure the enhanced ferroelectricity and shortened switching time. The co-doping strategy offers an effective avenue to control the defect state and improve the ferroelectric properties of HfO2 films.

Suppressing Structure Delamination for Enhanced Electrochemical Performance of Solid Oxide Cells.

Reversible solid oxide cells (rSOCs) have significant potential as efficient energy conversion and storage systems. Nevertheless, the practical application of their conventional air electrodes, such as La0.8Sr0.2MnO3-δ (LSM), Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), and PrBa0.8Ca0.2Co2O5+δ (PBCC), remains unsatisfactory due to interface delamination during prolonged electrochemical operation. Using micro-focusing X-ray absorption spectroscopy (µ-XAS), a decrease (increase) in the co-valence state from the electrode surface to the electrode/electrolyte interface is observed, leading to the above delamination. Utilizing the one-pot method to incorporate an oxygen-vacancy-enriched CeO2 electrode into these air electrodes, the uniform distribution of the Co valence state is observed, alleviating the structural delamination. PBCC-CeO2 electrodes exhibited a degradation rate of 0.095 mV h-1 at 650 °C during a nearly 500-h test as compared with 0.907 mV h-1 observed during the 135-h test for PBCC. Additionally, a remarkable increase in electrolysis current density from 636 to 934 mA cm-2 under 1.3 V and a maximum power density from 912 to 989 mW cm-2 upon incorporating CeO2 into PBCC is also observed. BSCF-CeO2 and LSM-CeO2 also show enhanced electrochemical performance and prolonged stability as compared to BSCF and LSM. This work offers a strategy to mitigate the structural delamination of conventional electrodes to boost the performance of rSOCs.

Three-dimensional ultrafast charge-density-wave dynamics in CuTe.

Charge density waves (CDWs) involved with electronic and phononic subsystems simultaneously are a common quantum state in solid-state physics, especially in low-dimensional materials. However, CDW phase dynamics in various dimensions are yet to be studied, and their phase transition mechanism is currently moot. Here we show that using the distinct temperature evolution of orientation-dependent ultrafast electron and phonon dynamics, different dimensional CDW phases are verified in CuTe. When the temperature decreases, the shrinking of c-axis length accompanied with the appearance of interchain and interlayer interactions causes the quantum fluctuations (QF) of the CDW phase until 220 K. At T < 220 K, the CDWs on the different ab-planes are finally locked with each other in anti-phase to form a CDW phase along the c-axis. This study shows the dimension evolution of CDW phases in one CDW system and their stabilized mechanisms in different temperature regimes.

High-Pressure Synthesis of Quadruple Perovskite Oxide CaCu3Cr2Re2O12 with a High Ferrimagnetic Curie Temperature.

An AA'3B2B'2O12-type quadruple perovskite oxide of CaCu3Cr2Re2O12 was synthesized at 18 GPa and 1373 K. Both an A- and B-site ordered quadruple perovskite crystal structure was observed, with the space group Pn-3. The valence states are verified to be CaCu32+Cr23+Re25+O12 by bond valence sum calculations and synchrotron X-ray absorption spectroscopy. The spin interaction among Cu2+, Cr3+, and Re5+ generates a ferrimagnetic transition with the Curie temperature (TC) at about 360 K. Moreover, electric transport properties and specific heat data suggest the presence of a half-metallic feature for this compound. The present study provides a promising quadruple perovskite oxide with above-room-temperature ferrimagnetism and possible half-metallic properties, which shows potential in the usage of spintronic devices.

Spin polarized Fe1-Ti pairs for highly efficient electroreduction nitrate to ammonia.

Electrochemical nitrate reduction to ammonia offers an attractive solution to environmental sustainability and clean energy production but suffers from the sluggish *NO hydrogenation with the spin-state transitions. Herein, we report that the manipulation of oxygen vacancies can contrive spin-polarized Fe1-Ti pairs on monolithic titanium electrode that exhibits an attractive NH3 yield rate of 272,000 µg h-1 mgFe-1 and a high NH3 Faradic efficiency of 95.2% at -0.4 V vs. RHE, far superior to the counterpart with spin-depressed Fe1-Ti pairs (51000 µg h-1 mgFe-1) and the mostly reported electrocatalysts. The unpaired spin electrons of Fe and Ti atoms can effectively interact with the key intermediates, facilitating the *NO hydrogenation. Coupling a flow-through electrolyzer with a membrane-based NH3 recovery unit, the simultaneous nitrate reduction and NH3 recovery was realized. This work offers a pioneering strategy for manipulating spin polarization of electrocatalysts within pair sites for nitrate wastewater treatment.

Antiferroelectricity-Induced Negative Thermal Expansion in Double Perovskite Pb2 CoMoO6.

Materials with negative thermal expansion (NTE) attract significant research attention owing to their unique physical properties and promising applications. Although ferroelectric phase transitions leading to NTE are widely investigated, information on antiferroelectricity-induced NTE remains limited. In this study, single-crystal and polycrystalline Pb2 CoMoO6 samples are prepared at high pressure and temperature conditions. The compound crystallizes into an antiferroelectric Pnma orthorhombic double perovskite structure at room temperature owing to the opposite displacements dominated by Pb2+ ions. With increasing temperature to 400 K, a structural phase transition to cubic Fm-3m paraelectric phase occurs, accompanied by a sharp volume contraction of 0.41%. This is the first report of an antiferroelectric-to-paraelectric transition-induced NTE in Pb2 CoMoO6 . Moreover, the compound also exhibits remarkable NTE with an average volumetric coefficient of thermal expansion αV = -1.33 × 10-5 K-1 in a wide temperature range of 30-420 K. The as-prepared Pb2 CoMoO6 thus serves as a prototype material system for studying antiferroelectricity-induced NTE.

High-energy all-solid-state lithium batteries enabled by Co-free LiNiO2 cathodes with robust outside-in structures.

A critical current challenge in the development of all-solid-state lithium batteries (ASSLBs) is reducing the cost of fabrication without compromising the performance. Here we report a sulfide ASSLB based on a high-energy, Co-free LiNiO2 cathode with a robust outside-in structure. This promising cathode is enabled by the high-pressure O2 synthesis and subsequent atomic layer deposition of a unique ultrathin LixAlyZnzOδ protective layer comprising a LixAlyZnzOδ surface coating region and an Al and Zn near-surface doping region. This high-quality artificial interphase enhances the structural stability and interfacial dynamics of the cathode as it mitigates the contact loss and continuous side reactions at the cathode/solid electrolyte interface. As a result, our ASSLBs exhibit a high areal capacity (4.65 mAh cm-2), a high specific cathode capacity (203 mAh g-1), superior cycling stability (92% capacity retention after 200 cycles) and a good rate capability (93 mAh g-1 at 2C). This work also offers mechanistic insights into how to break through the limitation of using expensive cathodes (for example, Co-based) and coatings (for example, Nb-, Ta-, La- or Zr-based) while still achieving a high-energy ASSLB performance.

Enhanced Exchange Bias in Epitaxial High-Entropy Oxide Heterostructures.

High-entropy oxides (HEOs) have gained significant interest in recent years due to their unique structural characteristics and potential to tailor functional properties. However, the electronic structure of the HEOs currently remains vastly unknown. In this work, combining magnetometry measurements, scanning transmission electron microscopy, and element-specific X-ray absorption spectroscopy, the electronic structure and magnetic properties of the perovskite-HEO La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 epitaxial thin films are systemically studied. It is found that enhanced magnetic frustration emerges from competing exchange interactions of the five transition-metal cations with energetically favorable half-filled/full-filled electron configurations, resulting in an unprecedented large vertical exchange bias effect in the single-crystalline films. Furthermore, our findings demonstrate that the La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 layer with a thickness down to 1 nm can be used as a pinning layer and strongly coupled with a ferromagnetic La0.7Sr0.3MnO3 layer, leading to a notable exchange bias and coercivity enhancement in a cooling field as small as 5 Oe. Our studies not only provide invaluable insight into the electronic structure of HEOs but also pave the way for a new era of large bias materials for spintronics devices.

Insights into Reversible Sodium Intercalation in a Novel Sodium-Deficient NASICON-Type Structure:Na3.40 □0.60 Co0.5 Fe0.5 V(PO4 )3.

The rational design of novel high-performance cathode materials for sodium-ion batteries is a challenge for the development of the renewable energy sector. Here, a new sodium-deficient NASICON phosphate, namely Na3.40 □0.60 Co0.5 Fe0.5 V(PO4 )3 , demonstrating the excellent electrochemical performance is reported. The presence of Co allows a third Na+ to participate in the reaction thus exhibiting a high reversible capacity of ≈155 mAh g-1 in the voltage range of 2.0-4.0 V versus Na+ /Na with a reversible single-phase mechanism and a small volume shrinkage of ≈5.97% at 4.0 V. 23 Na solid-state nuclear magnetic resonance (NMR) combined with ex situ X-ray diffraction (XRD) refinements provide evidence for a preferential Na+ insertion within the Na2 site. Furthermore, the enhanced sodium kinetics ascribed to Co-substitution is also confirmed in combination with electrochemical impedance spectroscopy (EIS), galvanostatic intermittent titration technique (GITT), and theoretical calculation.

Spin State Disproportionation in Insulating Ferromagnetic LaCoO3 Epitaxial Thin Films.

The origin of insulating ferromagnetism in epitaxial LaCoO3 films under tensile strain remains elusive despite extensive research efforts are devoted. Surprisingly, the spin state of its Co ions, the main parameter of its ferromagnetism, is still to be determined. Here, the spin state in epitaxial LaCoO3 thin films is systematically investigated to clarify the mechanism of strain-induced ferromagnetism using element-specific X-ray absorption spectroscopy and dichroism. Combining with the configuration interaction cluster calculations, it is unambiguously demonstrated that Co3+ in LaCoO3 films under compressive strain (on LaAlO3 substrate) is practically a low-spin state, whereas Co3+ in LaCoO3 films under tensile strain (on SrTiO3 substrate) have mixed high-spin and low-spin states with a ratio close to 1:3. From the identification of this spin state ratio, it is inferred that the dark strips observed by high-resolution scanning transmission electron microscopy indicate the position of Co3+ high-spin state, i.e., an observation of a spin state disproportionation in tensile-strained LaCoO3 films. This consequently explains the nature of ferromagnetism in LaCoO3 films. The study highlights the importance of spin state degrees of freedom, along with thin-film strain engineering, in creating new physical properties that do not exist in bulk materials.

Origin of the Seriously Limited Anionic Redox Reaction of Li-Rich Cathodes in Sulfide All-Solid-State Batteries.

Li-rich layered oxide (LLO) cathode materials with mixed cationic and anionic redox reactions display much higher specific capacity than other traditional layered oxide materials. However, the practical specific capacity of LLO during the first cycle in sulfide all-solid-state lithium-ion batteries (ASSLBs) is extremely low. Herein, the capacity contribution of each redox reaction in LLO during the first charging process is qualitatively and quantitatively analyzed by comprehensive electrochemical and structural measurements. The results demonstrate that the cationic redox of the LiTMO2 (TM = Ni, Co, Mn) phase is almost complete, while the anionic redox of the Li2MnO3 phase is seriously limited due to the sluggish transport kinetics and severe LLO/Li6PS5Cl interface reaction at high voltage. Therefore, the poor intrinsic conductivity and interface stability during the anionic redox jointly restrict the capacity release or delithiation/lithiation degree of LLO during the first cycle in sulfide ASSLBs. This study reveals the origin of the seriously limited anionic redox reaction in LLO, providing valuable guidance for the bulk and interface design of high-energy-density ASSLBs.

Highly Oxidative-Resistant Cyano-Functionalized Lithium Borate Salt for Enhanced Cycling Performance of Practical Lithium-Ion Batteries.

Lithium difluoro(oxalato) borate (LiDFOB) has been widely investigated in lithium-ion batteries (LIBs) owing to its advantageous thermal stability and excellent aluminum passivation property. However, LiDFOB tends to suffer from severe decomposition and generate a lot of gas species (e.g., CO2 ). Herein, a novel cyano-functionalized lithium borate salt, namely lithium difluoro(1,2-dihydroxyethane-1,1,2,2-tetracarbonitrile) borate (LiDFTCB), is innovatively synthesized as a highly oxidative-resistant salt to alleviate above dilemma. It is revealed that the LiDFTCB-based electrolyte enables LiCoO2 /graphite cells with superior capacity retention at both room and elevated temperatures (e.g., 80 % after 600 cycles) with barely any CO2 gas evolution. Systematic studies reveal that LiDFTCB tends to form thin and robust interfacial layers at both electrodes. This work emphasizes the crucial role of cyano-functionalized anions in improving cycle lifespan and safety of practical LIBs.

Unusual double ligand holes as catalytic active sites in LiNiO2.

Designing efficient catalyst for the oxygen evolution reaction (OER) is of importance for energy conversion devices. The anionic redox allows formation of O-O bonds and offers higher OER activity than the conventional metal sites. Here, we successfully prepare LiNiO2 with a dominant 3d8L configuration (L is a hole at O 2p) under high oxygen pressure, and achieve a double ligand holes 3d8L2 under OER since one electron removal occurs at O 2p orbitals for NiIII oxides. LiNiO2 exhibits super-efficient OER activity among LiMO2, RMO3 (M = transition metal, R = rare earth) and other unary 3d catalysts. Multiple in situ/operando spectroscopies reveal NiIII→NiIV transition together with Li-removal during OER. Our theory indicates that NiIV (3d8L2) leads to direct O-O coupling between lattice oxygen and *O intermediates accelerating the OER activity. These findings highlight a new way to design the lattice oxygen redox with enough ligand holes created in OER process.

Mo-Incorporated Magnetite Fe3 O4 Featuring Cationic Vacancies Enabling Fast Lithium Intercalation for Batteries.

Transition metal oxides (TMOs) as high-capacity electrodes have several drawbacks owing to their inherent poor electronic conductivity and structural instability during the multi-electron conversion reaction process. In this study, the authors use an intrinsic high-valent cation substitution approach to stabilize cation-deficient magnetite (Fe3 O4 ) and overcome the abovementioned issues. Herein, 5 at% of Mo4+ -ions are incorporated into the spinel structure to substitute octahedral Fe3+ -ions, featuring ≈1.7 at% cationic vacancies in the octahedral sites. This defective Fe2.93 ▫0.017 Mo0.053 O4 electrode shows significant improvements in the mitigation of capacity fade and the promotion of rate performance as compared to the pristine Fe3 O4 . Furthermore, physical-electrochemical analyses and theoretical calculations are performed to investigate the underlying mechanisms. In Fe2.93 ▫0.017 Mo0.053 O4 , the cationic vacancies provide active sites for storing Li+ and vacancy-mediated Li+ migration paths with lower energy barriers. The enlarged lattice and improved electronic conductivity induced by larger doped-Mo4+ yield this defective oxide capable of fast lithium intercalation. This is confirmed by a combined characterization including electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and density functional theory (DFT) calculation. This study provides a valuable strategy of vacancy-mediated reaction to intrinsically modulate the defective structure in TMOs for high-performance lithium-ion batteries.

Twisted oxide lateral homostructures with conjunction tunability.

Epitaxial growth is of significant importance over the past decades, given it has been the key process of modern technology for delivering high-quality thin films. For conventional heteroepitaxy, the selection of proper single crystal substrates not only facilitates the integration of different materials but also fulfills interface and strain engineering upon a wide spectrum of functionalities. Nevertheless, the lattice structure, regularity and crystalline orientation are determined once a specific substrate is chosen. Here, we reveal the growth of twisted oxide lateral homostructure with controllable in-plane conjunctions. The twisted lateral homostructures with atomically sharp interfaces can be composed of epitaxial "blocks" with different crystalline orientations, ferroic orders and phases. We further demonstrate that this approach is universal for fabricating various complex systems, in which the unconventional physical properties can be artificially manipulated. Our results establish an efficient pathway towards twisted lateral homostructures, adding additional degrees of freedom to design epitaxial films.

Photonic-Crafting of Non-Volatile and Rewritable Antiferromagnetic Spin Textures with Drastic Difference in Electrical Conductivity.

Antiferromagnetic spintronics is an emerging field of non-volatile data storage and information processing. The zero net magnetization and zero stray fields of antiferromagnetic materials eliminate interference between neighbor units, leading to high-density memory integrations. However, this invisible magnetic character at the same time also poses a great challenge in controlling and detecting magnetic states in antiferromagnets. Here, two antiferromagnetic spin states close in energy in strained BiFeO3 thin films at room temperature are discovered. It can be reversibly switched between these two non-volatile antiferromagnetic states by a moderate magnetic field and a non-contact optical approach. Importantly, the conductivity of the areas with each antiferromagnetic textures is drastically different. It is conclusively demonstrated the capability of optical writing and electrical reading of these newly discovered bistable antiferromagnetic states in the BiFeO3 thin films.

Presence of Delocalized Ti 3d Electrons in Ultrathin Single-Crystal SrTiO3.

Strontium titanate (STO), with a wide spectrum of emergent properties such as ferroelectricity and superconductivity, has received significant attention in the community of strongly correlated materials. In the strain-free STO film grown on the SrRuO3 buffer layer, the existing polar nanoregions can facilitate room-temperature ferroelectricity when the STO film thickness approaches 10 nm. Here we show that around this thickness scale, the freestanding STO films without the influence of a substrate show the tetragonal structure at room temperature, contrasting with the cubic structure seen in bulk form. The spectroscopic measurements reveal the modified Ti-O orbital hybridization that causes the Ti ion to deviate from its nominal 4+ valency (3d0 configuration) with excess delocalized 3d electrons. Additionally, the Ti ion in TiO6 octahedron exhibits an off-center displacement. The inherent symmetry lowering in ultrathin freestanding films offers an alternative way to achieve tunable electronic structures that are of paramount importance for future technological applications.

Extremely Fast Optical and Nonvolatile Control of Mixed-Phase Multiferroic BiFeO3 via Instantaneous Strain Perturbation.

Multiferroics-materials that exhibit coupled ferroic orders-are considered to be one of the most promising candidate material systems for next-generation spintronics, memory, low-power nanoelectronics and so on. To advance potential applications, approaches that lead to persistent and extremely fast functional property changes are in demand. Herein, it is revealed that the phase transition and the correlated ferroic orders in multiferroic BiFeO3 (BFO) can be modulated via illumination of single short/ultrashort light pulses. Heat transport simulations and ultrafast optical pump-probe spectroscopy reveal that the transient strain induced by light pulses plays a key role in determining the persistent final states. Having identified the diffusionless phase transformation features via scanning transmission electron microscopy, sequential laser pulse illumination is further demonstrated to perform large-area phase and domain manipulation in a deterministic way. The work contributes to all-optical and rapid nonvolatile control of multiferroicity, offering different routes while designing novel optoelectronics.

Mechanically tunable exchange coupling of Co/CoO bilayers on flexible muscovite substrates.

The employment of flexible muscovite substrates has given us the feasibility of applying strain to heterostructures dynamically by mechanical bending. In this study, this novel approach is utilized to investigate strain effects on the exchange coupling in ferromagnetic Co and anti-ferromagnetic CoO (Co/CoO) bilayers. Two different Co/CoO bilayer heterostructures were grown on muscovite substrates by oxide molecular beam epitaxy, with the CoO layer being purely (111)- and (100)-oriented. The strain-dependent exchange coupling effect can only be observed on Co/CoO(100)/mica but not on Co/CoO(111)/mica. The origin of this phenomenon is attributed to the anisotropic spin re-orientation induced by mechanical bending. The strain-dependent magnetic anisotropy of the bilayers determined by anisotropic magnetoresistance measurements confirms this conjecture. This study elucidates the fundamental understanding of how magnetic exchange coupling can be tuned by externally applied strain via mechanical bending and, hence, provides a novel approach for implementing flexible spintronic devices.