Structural Synthon Approach to the Study of Stacking Faults in the Layered Double Hydroxides of Lithium and Aluminum

A single layer of the Li‐Al layered double hydroxide (LDH) can be considered to be a structural synthon that can be stacked in a number of ways to give rise to the polytypes of the Li‐Al LDH family. The topotactic imbibition of lithium into gibbsite and bayerite precursors gives rise to crystalline 2H and 1M₁ polytypes respectively. In contrast the sample formed through a gel to crystallite route is found to be a 1M₁ polytype with stacking disorders whose local symmetry corresponds to the 1M₂ polytype. On heating, a solid‐solid 1M₁→1H polytype transformation is observed.     

Defect intergrowths in barium polytitanates: 2. BaTi5O11

High resolution electron microscopy has been used to investigate the structure of BaTi₅O₁₁. Single-phase materials were prepared from alkoxide precursors and studied using lattice imaging and microdiffraction techniques. Considerable structural disorder was observed in all the samples investigated. In general, isolated defects were observed. These results from a displacement of the close-packed layers of the structure giving some face-sharing of the Ti octahedra. However, in several regions of the samples, systematic stacking faults lead to the formation of a new polytypic structure. The paper describes the defect mechanisms, and relates these to the structure of the new polytype.     

An Atomic View of Cation Diffusion Pathways from Single‐Crystal Topochemical Transformations

The diffusion pathways of Li‐ions as they traverse cathode structures in the course of insertion reactions underpin many questions fundamental to the functionality of Li‐ion batteries. Much current knowledge derives from computational models or the imaging of lithiation behavior at larger length scales; however, it remains difficult to experimentally image Li‐ion diffusion at the atomistic level. Here, by using topochemical Li‐ion insertion and extraction to induce single‐crystal‐to‐single‐crystal transformations in a tunnel‐structured V₂O₅ polymorph, coupled with operando powder X‐ray diffraction, we leverage single‐crystal X‐ray diffraction to identify the sequence of lattice interstitial sites preferred by Li‐ions to high depths of discharge, and use electron density maps to create a snapshot of ion diffusion in a metastable phase. Our methods enable the atomistic imaging of Li‐ions in this cathode material in kinetic states and provide an experimentally validated angstrom‐level 3D picture of atomic pathways thus far only conjectured through DFT calculations.     

Crystal structure of a NIR‐Emitting DNA‐Stabilized Ag16 Nanocluster

DNA has been used as a scaffold to stabilize small, atomically monodisperse silver nanoclusters, which have attracted attention due to their intriguing photophysical properties. Herein, we describe the X‐ray crystal structure of a DNA‐encapsulated, near‐infrared emitting Ag₁₆ nanocluster (DNA–Ag₁₆NC). The asymmetric unit of the crystal contains two DNA–Ag₁₆NCs and the crystal packing between the DNA–Ag₁₆NCs is promoted by several interactions, such as two silver‐mediated base pairs between 3′‐terminal adenines, two phosphate–Ca²⁺–phosphate interactions, and π‐stacking between two neighboring thymines. Each Ag₁₆NC is confined by two DNA decamers that take on a horse‐shoe‐like conformation and is almost fully shielded from the solvent environment. This structural insight will aid in the determination of the structure/photophysical property relationship for this class of emitters and opens up new research opportunities in fluorescence imaging and sensing using noble‐metal clusters.     

Anion mediated polytype selectivity among the basic salts of Co(II)

Basic salts of Co(II) crystallize in the rhombohedral structure. Two different polytypes, 3R₁ and 3R₂, with distinct stacking sequences of the metal hydroxide slabs, are possible within the rhombohedral structure. These polytypes are generated by simple translation of successive layers by (2/3, 1/3, z) or (1/3, 2/3, z). The symmetry of the anion and the mode of coordination influences polytype selection. Cobalt hydroxynitrate crystallizes in the structure of the 3R₂ polytype while the hydroxytartarate, hydroxychloride and α-cobalt hydroxide crystallize in the structure of the 3R₁ polytype. Cobalt hydroxysulfate is turbostratically disordered. The turbostratic disorder is a direct consequence of the mismatch between the crystallographically defined interlayer sites generated within the crystal and the tetrahedral symmetry of the SO₄²⁻ ions.     

Structural Design of Ionic Conduction Paths in Molecular Crystals for Selective and Enhanced Lithium Ion Conduction

The molecular crystals [Li{N(SO₂CF₃)₂}{C₆H₄(OCH₃)₂}₂] and [Li{N(SO₂CF₃)₂}{C₆F₂H₂(OCH₃)₂}₂] with solid‐state lithium ion conductivity have been synthesized by the addition of two equivalents of 1,2‐dimethoxybenzene or 1,2‐difluoro‐4,5‐dimethoxybenzene to Li{N(SO₂CF₃)₂}, respectively. Single‐crystal X‐ray diffraction analysis revealed the formation of ionic conduction paths with an ordered arrangement of lithium ions in these crystal structures, afforded by the self‐ assembled stacking of molecular‐based channels consisting of N(SO₂CF₃)₂ anion and 1,2‐dimethoxybenzene frameworks as a result of intermolecular aromatic and hydrogen interactions. These compounds show selective lithium ion conductivity as the anions behave as a component unit of the conduction paths. The relationship between the crystal structure and ionic conductivity of the molecular crystals provides a clue to the development of novel solid electrolytes based on molecular crystals showing fast and selective lithium ion conduction.     

Direct Observation of Defect-Aided Structural Evolution in a Nickel-Rich Layered Cathode

Ni-rich LiNi_1−x−yMn_xCo_yO₂ (NMC) layered compounds are the dominant cathode for lithium ion batteries. The role of crystallographic defects on structure evolution and performance degradation during electrochemical cycling is not yet fully understood. Here, we investigated the structural evolution of a Ni-rich NMC cathode in a solid-state cell by in situ transmission electron microscopy. Antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon Li depletion, the APB extended across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases was detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition were aided by the low diffusion barriers of TM ions at planar defects. This work reveals the dynamical scenario of secondary phase evolution, helping unveil the origin of performance fading in Ni-rich NMC.     

Efforts towards Practical and Sustainable Li/Na‐Air Batteries

The Li‐O₂ batteries have attracted much attention due to their parallel theoretical energy density to gasoline. In the past 20 years, understanding and knowledge in Li‐O₂ battery have greatly deepened in elucidating the relationship between structure and performance. Our group has been focusing on the cathode engineering and anode protection strategy development in the past years, trying to make full use of the superiority of metal‐air batteries towards applications. In this review, we aim to retrospect our efforts in developing practical, sustainable metal‐air batteries. We will first introduce the basic working principle of Li‐O₂ batteries and our progresses in Li‐O₂ batteries with typical cathode designs and anode protection strategies, which have together promoted the large capacity, long life and low charge overpotential. We emphasize the designing art of carbon‐based cathodes in this part along with a short talk on all‐metal cathodes. The following part is our research in Na‐O₂ batteries including both cathode and anode optimizations. The differences between Li‐O₂ and Na‐O₂ batteries are also briefly discussed. Subsequently, our proof‐of‐concept work on Li‐N₂ battery, a new energy storage system and chemistry, is discussed with detailed information on the discharge product identification. Finally, we summarize our designed models and prototypes of flexible metal‐air batteries that are promising to be used in flexible devices to deliver more power.     

Properties and Structure of Spinel Li‐Mn‐O‐F Compounds for Cathode Materials of Secondary Lithium‐ion Battery

The spinel Li‐Mn‐O‐F compound cathode materials were synthesized by solid‐state reaction from calculated amounts LiOH‐H₂O, MnO₂(EMD) and LiF. The results of the electrochemical test demonstrated that these materials exhibited excellent electrochemical properties. It's initial capacity is ‐ 115 mAh.g¹ and reversible efficiency is about 100%. After 60 cycles, its capacity is still around 110 mAh.g¹ with nearly 100% reversible efficiency. The spinel Li‐Mn‐O‐F compound possibly has two structure models: interstitial model [Li]‐[Mn³⁺_xMn⁴⁺_2‐x]O₄F_δ, in which the fluorine is located on the interstice of crystal lattice, and substituted model [Li]‐[Mn³⁺_xMn⁴⁺_2‐x]O_4‐δF_δ, which the fluorine atom substituted the oxygen atom. The electrochemical result supports the interstitial model [Li][Mn³⁺_xMn⁴⁺_2‐x]O₄F_δ.     

Structural Synthon Approach to Predict the Possible Polytypes of Layered Double Hydroxides

The complete universe of possible polytypes of layered double hydroxides (LDH) is predicted on the basis of symmetry arguments. A single [MX₂] (X = OH) layer, also defined as a structural synthon, belongs to the layer group P$\bar{3}$ 2/m1. These layers can be stacked in such a way as to conserve the unique 3‐axis of the layer in the resultant crystal. The different stacking sequences that facilitate symmetry conservation, yield the different possible polytypes of rhombohedral and hexagonal symmetries. More polytypes can be envisaged by including stacking sequences that systematically destroy the principal symmetry elements of the structural synthon. Thereby, stacking sequences that destroy the 3‐axis, while retaining the 2‐axis, yield possible polytypes of monoclinic symmetry. The nitrate‐containing LDH of zinc and aluminum crystallizes in a faulted structure in which, the planar faults are shown to arise on account of stacking sequences whose local symmetry is monoclinic. This approach to polytype prediction expands on an earlier reported method by Bookin and Drits and is very general with important implications for other classes of layered materials.     

A new polytype of orthoboric acid,H3BO3‐3T

The crystal structure of H₃BO₃‐3T, a new trigonal polytype of orthoboric acid, consists of sheets of hydrogen‐bonded B(OH)₃ mol­ecules similar to those found in the triclinic structure of orthoboric acid, H₃BO₃‐2A. In each case, van der Waals forces connect the sheets. However, the stacking sequences of the sheets differ between the two polymorphs. In H₃BO₃‐3T (space group P3₂), the sheets are stacked in the repeating sequence ABC…, whereas in H₃BO₃‐2A (space group ), the sheets are stacked in the repeating sequence AB….     

Synthesis and electrochemical properties of Ca-doped LiNi<Subscript>0.8</Subscript>Co<Subscript>0.2</Subscript>O<Subscript>2</Subscript> cathode material for lithium ion battery

LiNi_0.8Co_0.2O₂ and Ca-doped LiNi_0.8Co_0.2O₂ cathode materials have been synthesized via a rheological phase reaction method. X-ray diffraction studies show that the Ca-doped material, and also the discharged electrode, maintains a hexagonal structure even when cycled in the range of 3.0–4.35 V (vs Li⁺/Li) after 100 cycles. Electrochemical tests show that Ca doping significantly improves the reversible capacity and cyclability. The improvement is attributed to the formation of defects caused by the partial occupancy of Ca²⁺ ions in lithium lattice sites, which reduce the resistance and thus improve the electrochemical properties.     

Eine neue,hexagonale Modifikation von AgNiO2

A New Hexagonal Modification of AgNiO₂ AgNiO₂ was prepared from a preoxidized coprecipitate of Ag₂O and Ni(OH)₂ followed by keeping at 550 °C under an oxygen pressure of 130 MPa. According to the powder and single crystal X‐ray analysis of the crystal structure (P6₃/mmc, Z = 2, a = b = 2.93653(3), c = 12.2369(1) Å), a new 2H‐polytype of AgNiO₂ had formed. Qualitatively, the magnetic properties correspond to those found for 3R‐AgNiO₂, while the resistivity is showing a different dependence on temperature.     

Possibility of superconductivity in intercalation compound related to MgB2

We investigated the electronic structure of MgB₂ and intercalation compounds, MgBX (X = Li, Be, C), with fully relaxed crystal structure by using density functional theory. The compounds MgBLi and MgBBe could be similar two‐band superconductors to MgB₂ because the Fermi surface crosses σ and π bands. Our results indicate that changing the lattice constants, hole or electron doping, and stacking of B? X effect the energy levels of the σ and π bands in MgBX compounds. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Crystal structure of the 6H BaCrO3 polytype

A product from the reaction between CrO₂ and Ba₂CrO₄ at 900°C under 60–65 kbar was found to be the six-layer polytype of BaCrO₃ from powder diffraction studies. A hexagonal black crystal obtained from this reaction was isolated for single crystal studies and structure determination. The crystal was found to possess a six-layer stacking sequence of BaO₃ layers with space group $\text{P6}{}_3\text{mmc}$ and had unit cell parameters a = 5.629(2), c = 13.698(6)Å, and Z = 6. The structure was determined from 936 independent reflections of which 693 were considered observed. Averaging equivalent reflections yielded 163 unique, observed reflections. Refinement of the structure by least-squares methods gave a conventional R value of 4.8% (R_w = 6.2%). The structure consists of a six-layer stacking sequence of close-packed BaO₃ layers containing tetravalent chromium in all the octahedral oxygen interstices. The compound was found to be isostructural with previously reported BaMO₃ phases.     

Transition‐Metal Dependent Cation Disorder in the Chiral Cubic AB(HCO2)3 Metal‐Organic Frameworks (A = Li or Na,B = Mn or Co)

This study examines the crystal structures of the AB(HCO₂)₃ (A = Li or Na and B = Mn or Co) metal‐organic frameworks, which we find to adopt a chiral cubic P2₁3 structure. This shows that the Li containing formates are isostructural with their Na analogues, extending the phase stability of this chiral architecture. The Mn containing compounds have a magnetic sublattice similar to β‐Mn, long of interest due to its highly frustrated antiferromagnetic coupling. In contrast the Co formates appear to have partially disordered alkali and transition metal cations, which prevents the formation of a clean β‐Mn‐like magnetic sublattice. We have also re‐examined the magnetic properties of NaMn(HCO₂)₃ finding it to be a simple paramagnet down to 2 K with only weak antiferromagnetic coupling.     

Concomitant polymorphic forms of 3‐cyclopropyl‐5‐(2‐hydrazinylpyridin‐3‐yl)‐1,2,4‐oxadiazole

The dipharmacophore compound 3‐cyclopropyl‐5‐(2‐hydrazinylpyridin‐3‐yl)‐1,2,4‐oxadiazole, C₁₀H₁₁N₅O, was studied on the assumption of its potential biological activity. Two concomitant polymorphs were obtained on crystallization from isopropanol solution and these were thoroughly studied. Identical conformations of the molecules are found in both structures despite the low difference in energy between the four possible conformers. The two polymorphs differ crucially with respect to their crystal structures. A centrosymmetric dimer formed due to both stacking interactions of the `head‐to‐tail' type and N—H…N(π) hydrogen bonds is the building unit in the triclinic structure. The dimeric building units form an isotropic packing. In the orthorhombic polymorphic structure, the molecules form stacking interactions of the `head‐to‐head' type, which results in their organization in a column as the primary basic structural motif. The formation of N—H…N(lone pair) hydrogen bonds between two neighbouring columns allows the formation of a double column as the main structural motif. The correct packing motifs in the two polymorphs could not be identified without calculations of the pairwise interaction energies. The triclinic structure has a higher density and a lower (by 0.60 kcal mol^?1) lattice energy according to periodic calculations compared to the orthorhombic structure. This allows us to presume that the triclinic form of 3‐cyclopropyl‐5‐(2‐hydrazinylpyridin‐3‐yl)‐1,2,4‐oxadiazole is the more stable.     

2,6‐Di­phenyl­pyridine‐4‐carboxyl­ic acid

The distinctive feature of the crystal structure of 2,6‐di­phenyl­pyridine‐4‐carboxyl­ic acid, C₁₈H₁₃NO₂, is the formation of intermolecular O—H?O hydrogen bonds that lead to the formation of centrosymmetric cyclic dimers with R(8) topology. Molecules related by translation along the b axis exhibit strong π–π stacking of aromatic rings, with an average interplanar distance of 3.3 Å.     

A Versatile Halide Ester Enabling Li‐Anode Stability and a High Rate Capability in Lithium–Oxygen Batteries

Li‐O₂ batteries are promising candidates for next‐generation high‐energy‐density battery systems. However, the main problems of Li–O₂ batteries include the poor rate capability of the cathode and the instability of the Li anode. Herein, an ester‐based liquid additive, 2,2,2‐trichloroethyl chloroformate, was introduced into the conventional electrolyte of a Li–O₂ battery. Versatile effects of this additive on the oxygen cathode and the Li metal anode became evident. The Li–O₂ battery showed an outstanding rate capability of 2005 mAh g^?1 with a remarkably decreased charge potential at a large current density of 1000 mA g^?1. The positive effect of the halide ester on the rate capacity is associated with the improved solubility of Li₂O₂ in the electrolyte and the increased diffusion rate of O₂. Furthermore, the ester promotes the formation of a solid–electrolyte interphase layer on the surface of the Li metal, which restrains the loss and volume change of the Li electrode during stripping and plating, thereby achieving a cycling stability over 900 h and a Li capacity utilization of up to 10 mAh cm^?2.