Crystal structures of 1,1'-bis-(carb-oxy-meth-yl)-4,4'-bipyridinium derivatives.

The crystal structures of 2-[1'-(carb-oxy-meth-yl)-4,4'-bi-pyridine-1,1'-diium-1-yl]acetate tetra-fluoro-borate, C14H13N2O4 +·BF4 - or (Hbcbpy)(BF4), and neutral 1,1'-bis-(carboxyl-atometh-yl)-4,4'-bi-pyridine-1,1'-diium (bcbpy), C14H20N2O8, are reported. The asymmetric unit of the (Hbcbpy)(BF4) consists of a Hbcbpy+ monocation, a BF4 - anion, and one-half of a water mol-ecule. The BF4 - anion is disordered. Two pyridinium rings of the Hbcbpy+ monocation are twisted at a torsion angle of 30.3 (2)° with respect to each other. The Hbcbpy monocation contains a carb-oxy-lic acid group and a deprotonated carboxyl-ate group. Both groups exhibit both a long and a short C-O bond. The cations are linked by inter-molecular hydrogen-bonding inter-actions between the carb-oxy-lic acid and the deprotonated carboxyl-ate group to give one-dimensional zigzag chains. The asymmetric unit of the neutral bcbpy consists of one-half of the bcbpy and two water mol-ecules. In contrast to the Hbcbpy+ monocation, the neutral bcbpy mol-ecule contains two pyridinium rings that are coplanar with each other and a carboxyl-ate group with similar C-O bond lengths. The mol-ecules are connected by inter-molecular hydrogen-bonding inter-actions between water mol-ecules and carboxyl-ate groups, forming a three-dimensional hydrogen-bonding network.

Crystal structure of dilithium biphenyl-4,4'-di-sulfonate dihydrate.

The asymmetric unit of the title compound, µ-biphenyl-4,4'-di-sulfonato-bis-(aqua-lithium), [Li2(C12H8O6S2)(H2O)2] or Li2[Bph(SO3)2](H2O)2, consists of an Li ion, half of the diphenyl-4,4'-di-sulfonate [Bph(SO3 -)2] ligand, and a water mol-ecule. The Li ion exhibits a four-coordinate tetra-hedral geometry with three oxygen atoms of the Bph(SO3 -)2 ligands and a water mol-ecule. The tetra-hedral LiO4 units, which are inter-connected by biphenyl moieties, form a layer structure parallel to (100). These layers are further connected by hydrogen-bonding inter-actions to yield a three-dimensional network.

Heterogeneous intercalated metal-organic framework active materials for fast-charging non-aqueous Li-ion capacitors.

Intercalated metal-organic frameworks (iMOFs) based on aromatic dicarboxylate are appealing negative electrode active materials for Li-based electrochemical energy storage devices. They store Li ions at approximately 0.8 V vs. Li/Li+ and, thus, avoid Li metal plating during cell operation. However, their fast-charging capability is limited. Here, to circumvent this issue, we propose iMOFs with multi-aromatic units selected using machine learning and synthesized via solution spray drying. A naphthalene-based multivariate material with nanometric thickness allows the reversible storage of Li-ions in non-aqueous Li metal cell configuration reaching 85% capacity retention at 400 mA g-1 (i.e., 30 min for full charge) and 20 °C compared to cycling at 20 mA g-1 (i.e., 10 h for full charge). The same material, tested in combination with an activated carbon-based positive electrode, enables a discharge capacity retention of about 91% after 1000 cycles at 0.15 mA cm-2 (i.e., 2 h for full charge) and 20 °C. We elucidate the charge storage mechanism and demonstrate that during Li intercalation, the distorted crystal structure promotes electron delocalization by controlling the frame vibration. As a result, a phase transition suppresses phase separation, thus, benefitting the electrode's fast charging behavior.

Mathematical model based on staircase structure for porous electrode impedance.

Mathematical models for porous electrode impedance have been widely used in energy conversion and storage. They are also utilized for obtaining the physicochemical dynamics, resulting in theoretical understanding and prediction in practical energy devices. The existing mathematical models are limited in their explanations. This limitation can be attributed to the separate consideration of simple (planar electrodes) and complex (porous electrodes) systems and the complexity of parameter distribution with non-uniform processes. Here, to address these limitations, we propose a mathematical model based on a staircase structure that calculates the individual interfacial impedance at each step in the depth direction, which helps not only in describing complex and straightforward systems but also in uniform and non-uniform processes in the form of a simple, seamless general equation. Our study includes mathematical derivations, interpretations of porous electrode impedance, and validation of the experimental data.

Positive Feedback Mechanism to Increase the Charging Voltage of Li-O2 Batteries.

The large overpotential of nonaqueous Li-O2 batteries when charging causes low round-trip efficiency and decomposition of the electrode materials and electrolyte. The origins of this overpotential have been enthusiastically explored to date; however, a full understanding has not yet been reached because of the complexity of multistep reaction mechanisms. Here, we applied structural and electrochemical analysis techniques to investigate the reaction step that results in the increase of the overpotential when charging. Rietveld refinement of ex situ powder X-ray diffraction showed that a Li-deficient phase of Li2O2, Li2-xO2, formed when discharging and was present over the course of charging. The galvanostatic intermittent titration technique revealed that the rate-determining process in the first step of charging was a solid-solution type of delithiation. The chemical diffusion coefficient of Li+ ions in Li2-xO2, DLi, decreases as the cell voltage increases, which in turn leads to a decrease in the oxidation rate of Li2-xO2. Under galvanostatic conditions, the deceleration of oxidation induces further increase of the cell voltage; therefore, an intrinsic mechanism of positive feedback to increase the cell voltage occurs in the first step. The results demonstrate that the continuity of the first step can be extended by the suppression of changes in any of the elements of the positive feedback loop, i.e., the oxidation rate, cell voltage, or DLi.

Low-Resistance Mechanism of Nanoflake Crystalline Aromatic Dicarboxylates with Selective Defects for Safe and Fast Charging Negative Electrodes.

Low resistance of Li-intercalated negative electrodes is important for the safe and fast charging required for large-scale batteries. Here, we demonstrated that nanosized two-dimensional crystalline aromatic dicarboxylate negative electrode materials synthesized via spray drying exhibit low internal resistances at approximately 0.7 V vs Li/Li+, while retaining flat potential profiles. The spray-dried sample with a hollow structure is crushed into nanoflakes during ink preparation for electrode coating and forms a uniform and highly dispersed electrode structure. The charge-discharge evaluation indicates that the nanoflake sample showed smaller charge-discharge polarization than the bulk sample with stable cycling characteristics, resulting in significant high-rate property enhancement. Charge-transfer resistance of the nanoflake sample exhibits the lowest value (ca. 2.2 Ω cm2) among those reported for existing intercalation electrodes (5.2 to 235 Ω cm2). In comparison of the negative electrodes, the estimated maximum current density without Li deposition (ca. 316 mA cm-2) is more than 1 order of magnitude higher than that for currently used graphite (ca. 11 mA cm-2) and is also higher than those for high-rate oxides (137-298 mA cm-2). The resistance-crystal correlation using multiple regression analysis predictions and its verification reveal that this low resistance is owing to an improved Li acceptability associated with selective structural defects induced by the loss of incorporated crystallized water during drying. The crystal plane exposed by the selective structural defects is perpendicular to electronic and ionic conduction directions inside the solid, resulting in improved kinetics. Therefore, the proposed negative electrode allows safe and fast charging, with easy scale-up and sustainable resources.

Ion Transport in Porous Electrodes Obtained by Impedance Using a Symmetric Cell with Predictable Low-Temperature Battery Performance.

The decline of lithium-ion battery (LIB) performance at low temperatures, caused by the nonuniform occurrence of electrochemical reactions during cycling and the resulting irreversible capacity loss, significantly hinders further LIB commercialization. Herein, we report the first solution by analyzing the impedance using symmetric cells in the absence of charge-transfer reactions to obtain a parameter quantitatively describing ion transport in porous electrodes and thus modeling the effects of nonuniform reaction occurrence. The reciprocal of ionic resistance in porous electrodes (Rion-1) is found to be positively correlated with capacity retention during low-temperature cycling and is approximated as the product of maximum capacitance related to electric double-layer formation (Cdl,max) and the associated frequency (f0). Consequently, these ion-transport parameters can be used to predict capacity retention during low-temperature cycling, and the adopted approach therefore can help to mitigate low-temperature LIB performance degradation and thus contribute to the fabrication of next-generation rechargeable batteries.

On/off switchable electronic conduction in intercalated metal-organic frameworks.

The electrical properties of metal-organic frameworks (MOF) have attracted attention for MOF as electronic materials. We report on/off switchable electronic conduction behavior with thermal responsiveness in intercalated MOF (iMOF) with layered structure, 2,6-naphthalene dicarboxylate dilithium, which was previously reported as a reversible Li-intercalation electrode material. The I-V response of the intercalated sample, which was prepared using a chemically reductive lithiation agent, exhibits current flow with sufficiently high electronic conductivity, even though it displays insulating characteristics in the pristine state. Calculations of band structure and electron hopping conduction indicate that electronic conduction occurs in the two-dimensional π-stacking naphthalene layers when the band gap is decreased to 0.99 eV and because of the formation of an anisotropic electron hopping conduction pathway by Li intercalation. The structure exhibiting electronic conductivity remains stable up to 200°C and reverts to an insulating structure, without collapsing, at 400°C, offering the potential for a shutdown switch for battery safety during thermal runaway or for heat-responsive on/off switching electronic devices.

Organic dicarboxylate negative electrode materials with remarkably small strain for high-voltage bipolar batteries.

As advanced negative electrodes for powerful and useful high-voltage bipolar batteries, an intercalated metal-organic framework (iMOF), 2,6-naphthalene dicarboxylate dilithium, is described which has an organic-inorganic layered structure of π-stacked naphthalene and tetrahedral LiO4 units. The material shows a reversible two-electron-transfer Li intercalation at a flat potential of 0.8 V with a small polarization. Detailed crystal structure analysis during Li intercalation shows the layered framework to be maintained and its volume change is only 0.33%. The material possesses two-dimensional pathways for efficient electron and Li(+) transport formed by Li-doped naphthalene packing and tetrahedral LiO3C network. A cell with a high potential operating LiNi(0.5)Mn(1.5)O4 spinel positive and the proposed negative electrodes exhibited favorable cycle performance (96% capacity retention after 100 cycles), high specific energy (300 Wh kg(-1)), and high specific power (5 kW kg(-1)). An 8 V bipolar cell was also constructed by connecting only two cells in series.

Reformation of organic dicarboxylate electrode materials for rechargeable batteries by molecular self-assembly.

We have found that the specific capacity of a Li-intercalated metal-organic framework (iMOF) electrode material, 2,6-naphthalene dicarboxylate dilithium, can be increased by narrowing the distance between naphthalene layers via ordering. The increase in specific capacity can be attributed to formation of more efficient electron and ion pathways in the framework.

Assessment of cervical myelopathy using transcranial magnetic stimulation and prediction of prognosis after laminoplasty.

STUDY DESIGN: This study investigated the clinical usefulness of motor-evoked potentials (MEPs) produced by transcranial magnetic stimulation of the brain for cervical myelopathy patients. OBJECTIVE: The purpose of this study was to determine the usefulness of MEPs for the assessment of the severity of myelopathy and prediction of the outcome of laminoplasty. SUMMARY OF BACKGROUND DATA: Magnetic stimulation has been widely used for examination of the descending excitatory motor pathways in the central nervous system, but little attention has been paid to cervical myelopathy. METHODS: We measured the MEPs of 56 patients who underwent surgery for cervical myelopathy. The MEPs from the abductor pollicis brevis, abductor digiti minimi, tibialis anterior, and abductor hallucis muscle were evoked by transcranial magnetic brain stimulation. The latency from the anterior horn cell of the spinal cord to the hand or foot muscles was also measured, with the F-value [(F + M - 1)/2] calculated. This was followed by estimation of the central motor conduction time (CMCT). Severity of clinical disability was scored on the basis of symptoms according to a modified ADL scale for cervical myelopathy of the Japanese Orthopedic Association (JOA) score. RESULTS: The average CMCT of the symptomatic side significantly correlated with the preoperative JOA score. The average CMCT of the symptomatic side significantly correlated with the 1-year postoperative JOA score. The average CMCT for patients with poor outcome was significantly longer than that for patients with good outcome. CMCT of 15 milliseconds or more in the upper extremities or that of 22 milliseconds or more in the lower extremities indicated poor prognosis. CONCLUSION: In patients with cervical myelopathy, the CMCT significantly correlated with the results of clinical assessment. These findings regarding the duration of CMCT may be useful parameters in spinal pathology for prediction of the outcome of surgical treatment.