Quinoid-Based Three-Dimensional Metal-Organic Framework Fe2(dhbq)3: Porosity, Electrical Conductivity, and Solid-State Redox Properties.

We report the synthesis, characterization, and electronic properties of the quinoid-based three-dimensional metal-organic framework [Fe2(dhbq)3]. The MOF was synthesized without using cations as a template, unlike other reported X2dhbq3-based coordination polymers, and the crystal structure was determined by using single-crystal X-ray diffraction. The crystal structure was entirely different from the other reported [Fe2(X2dhbq3)]2-; three independent 3D polymers were interpenetrated to give the overall structure. The absence of cations led to a microporous structure, investigated by N2 adsorption isotherms. Temperature dependence of electrical conductivity data revealed that it exhibited a relatively high electrical conductivity of 1.2 × 10-2 S cm-1 (Ea = 212 meV) due to extended d-π conjugation in a three-dimensional network. Thermoelectromotive force measurement revealed that it is an n-type semiconductor with electrons as the majority of charge carriers. Structural characterization and spectroscopic analyses, including SXRD, Mössbauer, UV-vis-NIR, IR, and XANES measurements, evidenced the occurrence of no mixed valency based on the metal and the ligand. [Fe2(dhbq)3] upon incorporating as a cathode material for lithium-ion batteries engendered an initial discharge capacity of 322 mAh/g.

Are Redox-Active Organic Small Molecules Applicable for High-Voltage (>4 V) Lithium-Ion Battery Cathodes?

While organic batteries have attracted great attention due to their high theoretical capacities, high-voltage organic active materials (> 4 V vs Li/Li+ ) remain unexplored. Here, density functional theory calculations are combined with cyclic voltammetry measurements to investigate the electrochemistry of croconic acid (CA) for use as a lithium-ion battery cathode material in both dimethyl sulfoxide and γ-butyrolactone (GBL) electrolytes. DFT calculations demonstrate that CA dilitium salt (CA-Li2 ) has two enolate groups that undergo redox reactions above 4.0 V and a material-level theoretical energy density of 1949 Wh kg-1 for storing four lithium ions in GBL-exceeding the value of both conventional inorganic and known organic cathode materials. Cyclic-voltammetry measurements reveal a highly reversible redox reaction by the enolate group at ≈4 V in both electrolytes. Battery-performance tests of CA as lithium-ion battery cathode in GBL show two discharge voltage plateaus at 3.9 and 3.1 V, and a discharge capacity of 102.2 mAh g-1 with no capacity loss after five cycles. With the higher discharge voltages compared to the known, state-of-the-art organic small molecules, CA promises to be a prime cathode-material candidate for future high-energy-density lithium-ion organic batteries.

A photo-curable gel electrolyte ink for 3D-printable quasi-solid-state lithium-ion batteries.

3D printing technologies have been adapted to enable the fabrication of lithium-ion batteries (LIBs), allowing flexible designs such as micro-scale 3D shapes. Here, we demonstrate 3D-printable gel electrolytes, printed at room temperature. The electrolyte gel solidified by UV irradiation maintains its structural integrity and high lithium-ion conductivity, enabling fully 3D-printed quasi-solid-state LIBs.

Electron-Conductive Metal-Organic Framework, Fe(dhbq)(dhbq = 2,5-Dihydroxy-1,4-benzoquinone): Coexistence of Microporosity and Solid-State Redox Activity.

Redox-active metal-organic frameworks (MOFs) have great potential for use as cathode materials in lithium-ion batteries (LIBs) with large capacities because the organic ligands can undergo multiple-electron redox processes. However, most MOFs are electrical insulators, limiting their application as electrode materials. Here, we report an electron-conductive MOF with a 2,5-dihydroxy-1,4-benzoquinone (dhbq) ligand, Fe(dhbq). This compound had an electrical conductivity of 5 × 10-6 S cm-1 at room temperature due to d-π interactions between the Fe ion and the ligand and the permanent microporosity. Fe(dhbq) had an initial discharge capacity of 264 mA h g-1, corresponding to the two-electron redox process of dhbq.

Disulfide-Bridged (Mo3S11) Cluster Polymer: Molecular Dynamics and Application as Electrode Material for a Rechargeable Magnesium Battery.

Exploring novel electrode materials is critical for the development of a next-generation rechargeable magnesium battery with high volumetric capacity. Here, we showed that a distinct amorphous molybdenum sulfide, being a coordination polymer of disulfide-bridged (Mo3S11) clusters, has great potential as a rechargeable magnesium battery cathode. This material provided good reversible capacity, attributed to its unique structure with high flexibility and capability of deformation upon Mg insertion. Free-terminal disulfide moiety may act as the active site for reversible insertion and extraction of magnesium.

Development of bipolar all-solid-state lithium battery based on quasi-solid-state electrolyte containing tetraglyme-LiTFSA equimolar complex.

The development of high energy-density lithium-ion secondary batteries as storage batteries in vehicles is attracting increasing attention. In this study, high-voltage bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex were prepared, and the performance of the device was evaluated. Via the successful production of double-layered and triple-layered high-voltage devices, it was confirmed that these stacked batteries operated properly without any internal short-circuits of a single cell within the package: Their plateau potentials (6.7 and 10.0 V, respectively) were two and three times that (3.4 V) of the single-layered device, respectively. Further, the double-layered device showed a capacity retention of 99% on the 200th cycle at 0.5 C, which is an indication of good cycling properties. These results suggest that bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex could readily produce a high voltage of 10 V.

Bipolar stacked quasi-all-solid-state lithium secondary batteries with output cell potentials of over 6 V.

Designing a lithium ion battery (LIB) with a three-dimensional device structure is crucial for increasing the practical energy storage density by avoiding unnecessary supporting parts of the cell modules. Here, we describe the superior secondary battery performance of the bulk all-solid-state LIB cell and a multilayered stacked bipolar cell with doubled cell potential of 6.5 V, for the first time. The bipolar-type solid LIB cell runs its charge/discharge cycle over 200 times in a range of 0.1-1.0 C with negligible capacity decrease despite their doubled output cell potentials. This extremely high performance of the bipolar cell is a result of the superior battery performance of the single cell; the bulk all-solid-state cell has a charge/discharge cycle capability of over 1500 although metallic lithium and LiFePO4 are employed as anodes and cathodes, respectively. The use of a quasi-solid electrolyte consisting of ionic liquid and Al2O3 nanoparticles is considered to be responsible for the high ionic conductivity and electrochemical stability at the interface between the electrodes and the electrolyte. This paper presents the effective applications of SiO2, Al2O3, and CeO2 nanoparticles and various Li(+) conducting ionic liquids for the quasi-solid electrolytes and reports the best ever known cycle performances. Moreover, the results of this study show that the bipolar stacked three-dimensional device structure would be a smart choice for future LIBs with higher cell energy density and output potential. In addition, our report presents the advantages of adopting a three-dimensional cell design based on the solid-state electrolytes, which is of particular interest in energy-device engineering for mobile applications.