A 3.2 V Binary Layered Oxide Cathode for Potassium-Ion Batteries.

Potassium-ion batteries (KIBs) can offer high energy density, cyclability, and operational safety while being economical due to the natural abundance of potassium. Utilizing graphite as an anode, suitable cathodes can realize full cells. Searching for potential cathodes, this work introduces P3-type K0.5Ni1/3Mn2/3O2 layered oxide as a potential candidate synthesized by a simple solid-state method. The material works as a 3.2 V cathode combining Ni redox at high voltage and Mn redox at low voltage and exhibits highly reversible K+ ion (de)insertion at ambient and elevated (40-50 °C) temperatures. First-principles calculations suggest the ground state in-plane Mn-Ni ordering in the MO2 sheets is strongly correlated to the K-content in the framework, leading to an interwoven and alternative row ordering of Ni-Mn in K0.5Ni1/3Mn2/3O2. Postmortem and electrochemical titration reveal the occurrence of a solid solution mechanism during K+ (de)insertion. The findings suggest that the Ni addition can effectively tune the electronic and structural properties of the cathode, leading to improved electrochemical performance. This work provides new insights in the quest to develop potential low-cost Co-free KIB cathodes for practical applications in stationary energy storage.

Entropy-Stabilized Layered K0.6Ni0.05Fe0.05Mg0.05Ti0.05Mn0.725O2 as a High-Rate and Stable Cathode for Potassium-Ion Batteries.

Mn-based layered oxides have been considered the most promising cathode candidates for cost-effective potassium-ion batteries (PIBs). Herein, equiatomic constituents of Ni, Fe, Mg, and Ti have been introduced into the transition metal layers of Mn-based layered oxide to design a high-entropy K0.6Ni0.05Fe0.05Mg0.05Ti0.05Mn0.0725O2 (HE-KMO, S = 1.17R). Consequently, the experimental results manifest that the layered structure of HE-KMO is more stable than conventional low-entropy K0.6MnO2 (LE-KMO, S = 0.66R) during successive cycling and even upon exposure to moisture. Diffraction and electrochemical measurements reveal that HE-KMO undergoes a solid-solution mechanism, contrary to the multistage phase transition processes typically exemplified in K0.6MnO2. Benefiting from the stabilized high-entropy layered framework and the solid-solution K+ storage mechanism, the entropy-stabilized HE-KMO not only demonstrates exceptional rate capability but also shows excellent cyclic stability. Notably, a capacity retention ratio of 86% after 3000 cycles can still be sustained at a remarkable current density of 5000 mA g-1.

Oxygenated Triazine-Heptazine Heterostructure Creates an Enormous Ascension to the Visible Light Photocatalytic Hydrogen Evolution Performance of Porous C3 N4 Nanosheets.

A highly efficient g-C3 N4 photocatalyst is developed by a novel one-pot thermal polymerization method under a salt fog environment generated by heating the aqueous solution of urea and mixed metal salts of NaCl/KCl, namely SF-CN. Thanks to the synergistic effect of the oxygenation and chemical etching of the salt fog, the obtained SF-CN is an oxygenated ultrathin porous carbon nitride with an intermolecular triazine-heptazine heterostructure, meanwhile, shows enlarged specific surface area, greatly enhanced absorption of visible light, narrowed band gap with a lower conduction band, and an increased photocurrent response due to the effective separation of photogenerated holes and electrons, comparing to those of pristine g-C3 N4 . The theoretical simulations further reveal that the triazine-heptazine heterostructure possesses better photocatalytic hydrogen evolution (PHE) capability than pure triazine and heptazine carbon nitrides. In turn, SF-CN demonstrates an excellent visible light PHE rate of 18.13 mmol h-1  g-1 , up to 259.00 times of that of pristine g-C3 N4 .

Honeycomb-Layered Oxides With Silver Atom Bilayers and Emergence of Non-Abelian SU(2) Interactions.

Honeycomb-layered oxides with monovalent or divalent, monolayered cationic lattices generally exhibit myriad crystalline features encompassing rich electrochemistry, geometries, and disorders, which particularly places them as attractive material candidates for next-generation energy storage applications. Herein, global honeycomb-layered oxide compositions, Ag2 M2 TeO6 ( M = Ni , Mg , etc $M = \rm Ni, Mg, etc$ .) exhibiting Ag $\rm Ag$ atom bilayers with sub-valent states within Ag-rich crystalline domains of Ag6 M2 TeO6 and Ag $\rm Ag$ -deficient domains of Ag 2 - x Ni 2 TeO 6 ${\rm Ag}_{2 - x}\rm Ni_2TeO_6$ ( 0 < x < 2 $0 < x < 2$ ). The Ag $\rm Ag$ -rich material characterized by aberration-corrected transmission electron microscopy reveals local atomic structural disorders characterized by aperiodic stacking and incoherency in the bilayer arrangement of Ag $\rm Ag$ atoms. Meanwhile, the global material not only displays high ionic conductivity but also manifests oxygen-hole electrochemistry during silver-ion extraction. Within the Ag $\rm Ag$ -rich domains, the bilayered structure, argentophilic interactions therein and the expected Ag $\rm Ag$ sub-valent states ( 1 / 2 + , 2 / 3 + $1/2+, 2/3+$ , etc.) are theoretically understood via spontaneous symmetry breaking of SU(2)× U(1) gauge symmetry interactions amongst 3 degenerate mass-less chiral fermion states, justified by electron occupancy of silver 4 d z 2 $4d_{z^2}$ and 5s orbitals on a bifurcated honeycomb lattice. This implies that bilayered frameworks have research applications that go beyond the confines of energy storage.

Cationic vacancies as defects in honeycomb lattices with modular symmetries.

Layered materials tend to exhibit intriguing crystalline symmetries and topological characteristics based on their two dimensional (2D) geometries and defects. We consider the diffusion dynamics of positively charged ions (cations) localized in honeycomb lattices within layered materials when an external electric field, non-trivial topologies, curvatures and cationic vacancies are present. The unit (primitive) cell of the honeycomb lattice is characterized by two generators, [Formula: see text] of modular symmetries in the special linear group with integer entries, corresponding to discrete re-scaling and rotations respectively. Moreover, applying a 2D conformal metric in an idealized model, we can consistently treat cationic vacancies as topological defects in an emergent manifold. The framework can be utilized to elucidate the molecular dynamics of the cations in exemplar honeycomb layered frameworks and the role of quantum geometry and topological defects not only in the diffusion process such as prediction of conductance peaks during cationic (de-)intercalation process, but also pseudo-spin and pseudo-magnetic field degrees of freedom on the cationic honeycomb lattice responsible for bilayers.

Mixed alkali-ion transport and storage in atomic-disordered honeycomb layered NaKNi2TeO6.

Honeycomb layered oxides constitute an emerging class of materials that show interesting physicochemical and electrochemical properties. However, the development of these materials is still limited. Here, we report the combined use of alkali atoms (Na and K) to produce a mixed-alkali honeycomb layered oxide material, namely, NaKNi2TeO6. Via transmission electron microscopy measurements, we reveal the local atomic structural disorders characterised by aperiodic stacking and incoherency in the alternating arrangement of Na and K atoms. We also investigate the possibility of mixed electrochemical transport and storage of Na+ and K+ ions in NaKNi2TeO6. In particular, we report an average discharge cell voltage of about 4 V and a specific capacity of around 80 mAh g-1 at low specific currents (i.e., < 10 mA g-1) when a NaKNi2TeO6-based positive electrode is combined with a room-temperature NaK liquid alloy negative electrode using an ionic liquid-based electrolyte solution. These results represent a step towards the use of tailored cathode active materials for "dendrite-free" electrochemical energy storage systems exploiting room-temperature liquid alkali metal alloy materials.

Honeycomb layered oxides: structure, energy storage, transport, topology and relevant insights.

The advent of nanotechnology has hurtled the discovery and development of nanostructured materials with stellar chemical and physical functionalities in a bid to address issues in energy, environment, telecommunications and healthcare. In this quest, a class of two-dimensional layered materials consisting of alkali or coinage metal atoms sandwiched between slabs exclusively made of transition metal and chalcogen (or pnictogen) atoms arranged in a honeycomb fashion have emerged as materials exhibiting fascinatingly rich crystal chemistry, high-voltage electrochemistry, fast cation diffusion besides playing host to varied exotic electromagnetic and topological phenomena. Currently, with a niche application in energy storage as high-voltage materials, this class of honeycomb layered oxides serves as ideal pedagogical exemplars of the innumerable capabilities of nanomaterials drawing immense interest in multiple fields ranging from materials science, solid-state chemistry, electrochemistry and condensed matter physics. In this review, we delineate the relevant chemistry and physics of honeycomb layered oxides, and discuss their functionalities for tunable electrochemistry, superfast ionic conduction, electromagnetism and topology. Moreover, we elucidate the unexplored albeit vastly promising crystal chemistry space whilst outlining effective ways to identify regions within this compositional space, particularly where interesting electromagnetic and topological properties could be lurking within the aforementioned alkali and coinage-metal honeycomb layered oxide structures. We conclude by pointing towards possible future research directions, particularly the prospective realisation of Kitaev-Heisenberg-Dzyaloshinskii-Moriya interactions with single crystals and Floquet theory in closely-related honeycomb layered oxide materials.

Cation Distributions and Magnetic Properties of Ferrispinel MgFeMnO4.

The crystal structure and magnetic properties of the cubic spinel MgFeMnO4 were studied by using a series of in-house techniques along with large-scale neutron diffraction and muon spin rotation spectroscopy in the temperature range between 1.5 and 500 K. The detailed crystal structure is successfully refined by using a cubic spinel structure described by the space group Fd3̅m. Cations within tetrahedral A and octahedral B sites of the spinel were found to be in a disordered state. The extracted fractional site occupancies confirm the presence of antisite defects, which are of importance for the electrochemical performance of MgFeMnO4 and related battery materials. Neutron diffraction and muon spin spectroscopy reveal a ferrimagnetic order below TC = 394.2 K, having a collinear spin arrangement with antiparallel spins at the A and B sites, respectively. Our findings provide new and improved understanding of the fundamental properties of the ferrispinel materials and of their potential applications within future spintronics and battery devices.

Magnetism and ion diffusion in honeycomb layered oxide [Formula: see text].

In the quest for developing novel and efficient batteries, a great interest has been raised for sustainable K-based honeycomb layer oxide materials, both for their application in energy devices as well as for their fundamental material properties. A key issue in the realization of efficient batteries based on such compounds, is to understand the K-ion diffusion mechanism. However, investigation of potassium-ion (K[Formula: see text]) dynamics in materials using e.g. NMR and related techniques has so far been very challenging, due to its inherently weak nuclear magnetic moment, in contrast to other alkali ions such as lithium and sodium. Spin-polarised muons, having a high gyromagnetic ratio, make the muon spin rotation and relaxation ([Formula: see text]SR) technique ideal for probing ions dynamics in these types of energy materials. Here we present a study of the low-temperature magnetic properties as well as K[Formula: see text] dynamics in honeycomb layered oxide material [Formula: see text] using mainly the [Formula: see text]SR technique. Our low-temperature [Formula: see text]SR results together with complementary magnetic susceptibility measurements find an antiferromagnetic transition at [Formula: see text] K. Further [Formula: see text]SR studies performed at higher temperatures reveal that potassium ions (K[Formula: see text]) become mobile above 200 K and the activation energy for the diffusion process is obtained as [Formula: see text] meV. This is the first time that K[Formula: see text] dynamics in potassium-based battery materials has been measured using [Formula: see text]SR. Assisted by high-resolution neutron diffraction, the temperature dependence of the K-ion self diffusion constant is also extracted. Finally our results also reveal that K-ion diffusion occurs predominantly at the surface of the powder particles. This opens future possibilities for potentially improving ion diffusion as well as K-ion battery device performance using nano-structuring and surface coatings of the particles.

An idealised approach of geometry and topology to the diffusion of cations in honeycomb layered oxide frameworks.

Honeycomb layered oxides are a novel class of nanostructured materials comprising alkali or coinage metal atoms intercalated into transition metal slabs. The intricate honeycomb architecture and layered framework endows this family of oxides with a tessellation of features such as exquisite electrochemistry, unique topology and fascinating electromagnetic phenomena. Despite having innumerable functionalities, these materials remain highly underutilised as their underlying atomistic mechanisms are vastly unexplored. Therefore, in a bid to provide a more in-depth perspective, we propose an idealised diffusion model of the charged alkali cations (such as lithium, sodium or potassium) in the two-dimensional (2D) honeycomb layers within the multi-layered crystal of honeycomb layered oxide frameworks. This model not only explains the correlation between the excitation of cationic vacancies (by applied electromagnetic fields) and the Gaussian curvature deformation of the 2D surface, but also takes into consideration, the quantum properties of the cations and their inter-layer mixing through quantum tunnelling. Through this work, we offer a novel theoretical framework for the study of multi-layered materials with 2D cationic diffusion currents, as well as providing pedagogical insights into the role of topological phase transitions in these materials in relation to Brownian motion and quantum geometry.

High-voltage honeycomb layered oxide positive electrodes for rechargeable sodium batteries.

Honeycomb layered oxides from Na2Ni2-xCoxTeO6 family were assessed for use as positive electrodes in rechargeable sodium batteries at ambient and elevated temperatures using ionic liquids. Substitution of nickel with cobalt increases the discharge voltage to nearly 4 V (versus Na+/Na), surpassing the average voltages of most Na based layered oxide positive electrodes.

Bendable Network Built with Ultralong Silica Nanowires as a Stable Separator for High-Safety and High-Power Lithium-Metal Batteries.

Separators are key safety components for electrochemical energy storage systems. However, the intrinsic poor wettability with electrolyte and low thermal stability of commercial polyolefin separators cannot meet the requirements of the ever-expanding market for high-power, high-energy, and high-safety power systems, such as lithium-metal, lithium-sulfur, and lithium-ion batteries. In this study, scalable bendable networks built with ultralong silica nanowires (SNs) are developed as stable separators for both high-safety and high-power lithium-metal batteries. The three-dimensional porous nature (porosity of 73%) and the polar surface of the obtained SNs separators endue a much better electrolyte wettability, larger electrolyte uptake ratio (325%), higher electrolyte retention ratio (63%), and ∼7 times higher ionic conductivity than that of commercial polypropylene (PP) separators. Moreover, the pore-rich structure of the SNs separator can aid in evenly distributing lithium and, in turn, suppress the uncontrollable growth of lithium dendrites to a certain degree. Furthermore, the pure inorganic structure endows the SNs separators with excellent chemical and electrochemical stabilities even at elevated temperatures, as well as excellent thermal stability up to 700 °C. This work underpins the utilization of SNs separators as a rational choice for developing high-performance batteries with a metallic lithium anode.

Sulfur in Mesoporous Tungsten Nitride Foam Blocks: A Rational Lithium Polysulfide Confinement Experimental Design Strategy Augmented by Theoretical Predictions.

To enhance the utilization of sulfur in lithium-sulfur batteries, three-dimensional tungsten nitride (WN) mesoporous foam blocks are designed to spatially localize the soluble Li2S6 and Li2S4 within the pore spaces. Meanwhile, the chemisorption behaviors of polysulfides and the capability of WN as an effective confiner are systematically investigated through density functional theory calculations and experimental studies. The theoretical calculations reveal a decrease in chemisorption strength between WN and the soluble polysulfides (Li2S8 > Li2S6 > Li2S4), while the interactions between WN and the insoluble Li2S2/Li2S show a high chemisorption strength of ca. 3 eV. Validating theoretical insights through electrochemical measurements further manifest that the assembled battery configurations with sulfur cathode confined in the thickest WN blocks exhibit the best rate capabilities (1090 and 510 mAh g-1 at 0.5C and 5C, respectively) with the highest initial Coulombic efficiency of 90.5%. Moreover, a reversible capacity of 358 mAh g-1 is maintained with a high Coulombic efficiency approaching to 100%, even after 500 cycles at 2C. As guided by in silico design, this work not only provides an effective strategy to improve the retentivity of polysulfides but also underpins that properly architectured WN can be effective retainers of polysulfides.

A high voltage honeycomb layered cathode framework for rechargeable potassium-ion battery: P2-type K2/3Ni1/3Co1/3Te1/3O2.

The designing of high voltage cathode materials is critical for the advancement of potassium-ion (K-ion) battery. Herein, we present a new honeycomb framework P2-type K2/3Ni1/3Co1/3Te1/3O2 (or equivalently written as K2NiCoTeO6) which exhibits the highest voltage on record (beyond 4 V versus K+/K) for layered cathode materials. This work will allow for the further development of, particularly, high voltage layered cathodes for K-ion battery.

Rechargeable potassium-ion batteries with honeycomb-layered tellurates as high voltage cathodes and fast potassium-ion conductors.

Rechargeable potassium-ion batteries have been gaining traction as not only promising low-cost alternatives to lithium-ion technology, but also as high-voltage energy storage systems. However, their development and sustainability are plagued by the lack of suitable electrode materials capable of allowing the reversible insertion of the large potassium ions. Here, exploration of the database for potassium-based materials has led us to discover potassium ion conducting layered honeycomb frameworks. They show the capability of reversible insertion of potassium ions at high voltages (~4 V for K2Ni2TeO6) in stable ionic liquids based on potassium bis(trifluorosulfonyl) imide, and exhibit remarkable ionic conductivities e.g. ~0.01 mS cm-1 at 298 K and ~40 mS cm-1 at 573 K for K2Mg2TeO6. In addition to enlisting fast potassium ion conductors that can be utilised as solid electrolytes, these layered honeycomb frameworks deliver the highest voltages amongst layered cathodes, becoming prime candidates for the advancement of high-energy density potassium-ion batteries.

Anti-site mixing governs the electrochemical performances of olivine-type MgMnSiO4 cathodes for rechargeable magnesium batteries.

Rechargeable magnesium batteries are deemed as the next-generation secondary battery systems because of their high theoretical capacity and the terrestrial abundance of magnesium, which is used as the anode in these batteries. The cathode material is an important factor to improve the energy density of the magnesium batteries. In this study, we investigate olivine-type MgMnSiO4 cathode materials owing to their high theoretical capacity (>300 mA h g(-1)). The low-temperature synthesis of MgMnSiO4 suppresses anti-site mixing between Mg and Mn, which drastically improves the charge-discharge capacities of the magnesium battery cathode. Our results show that the suppression of the degree of anti-site mixing between Mg and Mn enhances the diffusion of Mg(2+) during magnesium (de)insertion, and therefore, it is a dominant factor that affects the electrochemical performance of olivine-type MgMnSiO4.

Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution.

Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances.

High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements.

Rechargeable magnesium batteries are poised to be viable candidates for large-scale energy storage devices in smart grid communities and electric vehicles. However, the energy density of previously proposed rechargeable magnesium batteries is low, limited mainly by the cathode materials. Here, we present new design approaches for the cathode in order to realize a high-energy-density rechargeable magnesium battery system. Ion-exchanged MgFeSiO4 demonstrates a high reversible capacity exceeding 300 Ah · g(-1) at a voltage of approximately 2.4 V vs. Mg. Further, the electronic and crystal structure of ion-exchanged MgFeSiO4 changes during the charging and discharging processes, which demonstrates the (de)insertion of magnesium in the host structure. The combination of ion-exchanged MgFeSiO4 with a magnesium bis(trifluoromethylsulfonyl)imide-triglyme electrolyte system proposed in this work provides a low-cost and practical rechargeable magnesium battery with high energy density, free from corrosion and safety problems.