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.

An overview of hydroxy-based polyanionic cathode insertion materials for metal-ion batteries.

Rechargeable batteries based on Li-ion and post Li-ion chemistry have come a long way since their inception in the early 1980s. The last four decades have witnessed steady development and discovery of myriads of cathode materials taking into account their processing, economy, and performance along with ecological sustainability. Though oxides rule the battery sector with their high energy and power density, polyanionic insertion compounds work as gold mines for designing insertion compounds with rich structural diversity leading to tuneable redox potential coupled with high structural/chemical/thermal stability. The scope of polyanionic compounds can be taken a step further by combining two or more different types of polyanions to get suites of mixed polyanionic materials. While most cathodes are built with metal polyhedra constituted by oxygen (MOm|XOm, M = 3d metals, X = P, S, Si, B, W, etc., m = 3-6), in some cases, selected oxygen sites can form bonding with hydrogen to form OH/H2O ligands. It can lead to the family of hydroxy-based mixed-polyanionic cathode materials. The presence of hydroxy components can affect the crystal structure, local chemical bonding, and electronic, magnetic, diffusivity and electrochemical properties. Employing a mineralogical survey, the current review renders a sneak peek on various hydroxy-based polyanionic cathode materials for Li-ion and post Li-ion batteries. Their crystal structure, and electrochemical properties have been overviewed to outline future research focus and scope for real-life application.

Fast operando X-ray pair distribution function using the DRIX electrochemical cell.

In situ electrochemical cycling combined with total scattering measurements can provide valuable structural information on crystalline, semi-crystalline and amorphous phases present during (dis)charging of batteries. In situ measurements are particularly challenging for total scattering experiments due to the requirement for low, constant and reproducible backgrounds. Poor cell design can introduce artefacts into the total scattering data or cause inhomogeneous electrochemical cycling, leading to poor data quality or misleading results. This work presents a new cell design optimized to provide good electrochemical performance while performing bulk multi-scale characterizations based on total scattering and pair distribution function methods, and with potential for techniques such as X-ray Raman spectroscopy. As an example, the structural changes of a nanostructured high-capacity cathode with a disordered rock-salt structure and composition Li4Mn2O5 are demonstrated. The results show that there is no contribution to the recorded signal from other cell components, and a very low and consistent contribution from the cell background.

Cubic Sodium Cobalt Metaphosphate [NaCo(PO3)3] as a Cathode Material for Sodium Ion Batteries.

Cubic-framework sodium cobalt-based metaphosphate NaCo(PO3)3 was recently demonstrated to be an attractive Na+ cationic conductor. It can be potentially used in the next-generation rechargeable Na ion batteries. The crystal structure and electrical conductivity were studied and found to have a three-dimensional framework with interconnecting tunnels for Na+ migration ( J. Solid State Electrochem. , 2016 , 20 , 1241 ). This inspired us to study the electrochemical (de)intercalation behavior of Na+ in the NaCo(PO3)3 assuming a cubic Pa3̅ framework. Herein, synergizing experimental and computational tools, we present the first report on the electrochemical activity and Na+ diffusion pathway analysis of cubic NaCo(PO3)3 prepared via conventional solid-state route. The electrochemical analyses reveal NaCo(PO3)3 to be an active sodium insertion material with well-defined reversible Co3+/Co2+ redox activity centered at 3.3 V (vs Na/Na+). Involving a solid-solution redox mechanism, close to 0.7 Na+ per formula unit can be reversibly extracted. This experimental finding is augmented with bond valence site energy (BVSE) modeling to clarify Na+ migration in cubic NaCo(PO3)3. BVSE analyses suggest feasible Na+ migration with moderate energy barrier of 0.68 eV. Cubic NaCo(PO3)3 forms a 3.3 V sodium insertion material.

Synthesis and Characterization of the LiMnBO3-LiCoBO3 Solid Solution and Its Use as a Lithium-Ion Cathode Material.

A complete solid solution of m-Li(Mn1-xCox)BO3 has been successfully synthesized for the first time with the idea of improving the average potential versus m-LiMnBO3. These compounds have been obtained by a multiple-step process. Interestingly, transmission electron microscopy results indicate that the C2/c space group previously reported for m-LiMBO3 (M = Mn, Co) cannot describe m-Li(Mn1-xCox)BO3 compounds. Each material shows electrochemical activity, without in situ carbon coating. Despite a large polarization, we report a capacity of almost 60 mAh/g at the first discharge at C/20 rate with good stability up to five cycles for LiMn0.7Co0.3BO3.

Electrochemical synthesis of a lithium-rich rock-salt-type oxide Li5W2O7 with reversible deintercalation properties.

Starting from the ribbon structure Li2W2O7, the lithium-rich phase Li5W2O7 with an ordered rock-salt-type structure has been synthesized, through a topotactic irreversible reaction, using both electrochemistry and soft chemistry. In contrast to Li2W2O7, the lithium-rich oxide Li5W2O7 shows reversible deintercalation properties of two lithium molecules per formula unit: a stable reversible capacity of 110 mAh/g at 1.70 V is maintained after 10 cycles. The exploration of the lithium mobility in this system shows that Li2W2O7 is a cationic conductor with σ = 4.10(-4) S/cm at 400 °C and Ea = 0.5 eV.

A3Ti5NbO14 (A = H, Li and K) family: ionic exchange, physical and electrochemical properties.

A new layered titanoniobate, Li3Ti5NbO14, a member of the AxM2nO4n+2 family, has been synthesized using a molten salt reaction between H3Ti5NbO14 and an eutectic mixture of LiOH and LiNO3. This compound crystallizes in the P21/m space group with a = 9.273(15) Å, b = 3.788(6) Å, c = 8.871(3) Å, and ß = 114.33(1)°, as determined by 3D electron diffraction single crystal analysis. It exhibits [Ti5NbO14]3- layers similar to K3Ti5NbO14, but differs from the latter by a 'parallel configuration' of its [Ti5NbO5]3- ribbons between the two successive layers. The topotactic character of the reaction suggests that exfoliation plays a prominent role in the synthesis of this new form. This new phase intercalates reversibly 2 lithium through a first-order transformation leading to a capacity of 100 mA h g-1 at a potential of 1.67 V vs. Li/Li+.

Effect of the boron element in a Li-P-S system.

Lithium-ion batteries are nowadays a mature technology for energy storage. However, some safety problems have been identified during their operation in high power applications such as fire incidents in electric vehicles. The most promising solution to improve the safety of lithium-ion batteries is replacing the current organic liquid based electrolytes with solid electrolytes. In this context, new solid electrolytes having chemical and electrochemical stability with high ionic conductivity need to be discovered. Therefore, in the present study, a new LGPS-type structural domain is highlighted for the Li-B-P-S system. Ionic conductivities of up to 10-4 S cm-1 have been achieved for prepared solid electrolytes in the Li-B-P-S system, and higher stability against lithium metal as compared to Li10GeP2S12. These solid electrolytes also show better electrochemical characteristics in all solid-state batteries.

Facile synthesis and phase stability of Cu-based Na2Cu(SO4)2·xH2O (x = 0-2) sulfate minerals as conversion type battery electrodes.

Mineral exploration forms a key approach for unveiling functional battery electrode materials. The synthetic preparation of naturally found minerals and their derivatives can aid in designing of new electrodes. Herein, saranchinaite Na2Cu(SO4)2 and its hydrated derivative kröhnkite Na2Cu(SO4)2·2H2O bisulfate minerals have been prepared using a facile spray drying route for the first time. The phase stability relation during the (de)hydration process was examined synergising in situ X-ray diffraction and thermochemical studies. Kröhnkite forms the thermodynamically stable phase as the hydration of saranchinaite to kröhnkite is highly exothermic (-51.51 ± 0.63 kJ mol-1). Structurally, kröhnkite offers a facile 2D pathway for Na+ ion migration resulting in 20 times higher total conductivity than saranchinaite at 60 °C. Both compounds exhibited a conversion redox mechanism for Li-ion storage with the first discharge capacity exceeding 650 mA h g-1 (at 2 mA g-1vs. Li+/Li) upon discharge up to 0.05 V. Post-mortem analysis revealed that the presence of metallic Cu in the discharged state is responsible for high irreversibility during galvanostatic cycling. This study reaffirms the exploration of Cu-based polyanionic sulfates, which while having limited (de)insertion properties, can be harnessed for conversion-based electrode materials for batteries.

Redox Activity of Sodium Vanadium Oxides towards Oxidation in Na Ion Batteries.

The search for new materials that could be used as electrode material for Na-ion batteries is one of the most challenging issues of today. Many transition metal oxide families as well as transition metal polyanionic frameworks have been proposed over the last five years. In this work, we report the sodium extraction from Na2V3O7, which is a tunnel type structure built of [V3O7]2−∞ nanotubes held by sodium ions. We report a reversible charge capacity of 80 mAh/g at 2.8 V vs. Na⁺/Na due to the V5+/V4+ redox activity. No oxygen redox activity has been observed for this material nor for the vanadium (5+) oxide Na4V2O7.

CuFe2S3 as electrode material for Li-ion batteries.

Electrochemical performances of the isocubanite CuFe2S3 tested as electrode material for Li-ion batteries have been investigated. A first discharge capacity of 860 mA h g-1 shows a conversion process leading to Li2S, copper and iron nanoparticles. Interestingly, a reversible capacity of 560 mA h g-1 at 1.5 V is demonstrated with good cyclability up to 30 cycles.

Intermolecular interactions in AST zeolites through 14N NMR and DFT calculations.

The structure of the silica AST zeolites (octadecasil) synthesized in fluoride medium using tetramethylammonium (TMA) as the organic structure-directing agent has been reinvestigated using 14N NMR quadrupolar parameters and DFT calculations. The value of the experimental 14N quadrupolar coupling constant (CQ = 27 kHz) is larger than expected for a TMA cation possessing a high degree of motion. The analysis of a DFT-optimized octadecasil cluster along with the comparison between measured and calculated 14N NMR parameters demonstrate the presence of weak C-H...O hydrogen bonds between the TMA in the [46612] cages and the silica skeleton. These intermolecular interactions can be related to the presence of Si...F tetrel bonds within the [46] cages. These new results provide additional information with regard to the formation mechanisms and structure of the octadecasil zeolites.

Copper hydroxydiphosphate with a one-dimensional arrangement of copper polyhedra: Cu3[P2O6OH]2.

A new copper hydroxydiphosphate Cu3(P2O6OH)2 was synthesized, by soft chemistry. The crystal structure was solved ab initio from X-ray powder diffraction data in the triclinic space group P. The structure is built up from [Cu3O10]infinity zigzag chains linked by P2O6(OH) groups to form a tridimensional framework. The [Cu3O10]infinity chains consist of edge-sharing polyhedra. The structure contains two sorts of copper polyhedra: one CuO6 octahedron and two CuO5 pyramids. Magnetization measurements confirm the presence of divalent copper and suggest antiferromagnetic interactions at low temperature.