An XPS Study of Electrolytes for Li-Ion Batteries in Full Cell LNMO vs Si/Graphite.

Two different types of electrolytes (co-solvent and multi-salt) are tested for use in high voltage LiNi0.5Mn1.5O4||Si/graphite full cells and compared against a carbonate-based standard LiPF6 containing electrolyte (baseline). Ex situ postmortem XPS analysis on both anodes and cathodes over the life span of the cells reveals a continuously growing SEI and CEI for the baseline electrolyte. The cells cycled in the co-solvent electrolyte exhibited a relatively thick and long-term stable CEI (on LNMO), while a slowly growing SEI was determined to form on the Si/graphite. The multi-salt electrolyte offers more inorganic-rich SEI/CEI while also forming the thinnest SEI/CEI observed in this study. Cross-talk is identified in the baseline electrolyte cell, where Si is detected on the cathode, and Mn is detected on the anode. Both the multi-salt and co-solvent electrolytes are observed to substantially reduce this cross-talk, where the co-solvent is found to be the most effective. In addition, Al corrosion is detected for the multi-salt electrolyte mainly at its end-of-life stage, where Al can be found on both the anode and cathode. Although the co-solvent electrolyte offers superior interface properties in terms of the limitation of cross-talk, the multi-salt electrolyte offers the best overall performance, suggesting that interface thickness plays a superior role compared to cross-talk. Together with their electrochemical cycling performance, the results suggest that multi-salt electrolyte provides a better long-term passivation of the electrodes for high-voltage cells.

Design Principles of Quinone Redox Systems for Advanced Sulfide Solid-State Organic Lithium Metal Batteries.

The emergence of solid-state battery technology presents a potential solution to the dissolution challenges of high-capacity small molecule quinone redox systems. Nonetheless, the successful integration of argyrodite-type Li6PS5Cl, the most promising solid-state electrolyte system, and quinone redox systems remains elusive due to their inherent reactivity. Here, a library of quinone derivatives is selected as model electrode materials to ascertain the critical descriptors governing the (electro)chemical compatibility and subsequently the performances of Li6PS5Cl-based solid-state organic lithium metal batteries (LMBs). Compatibility is attained if the lowest unoccupied molecular orbital level of the quinone derivative is sufficiently higher than the highest occupied molecular orbital level of Li6PS5Cl. The energy difference is demonstrated to be critical in ensuring chemical compatibility during composite electrode preparation and enable high-efficiency operation of solid-state organic LMBs. Considering these findings, a general principle is proposed for the selection of quinone derivatives to be integrated with Li6PS5Cl, and two solid-state organic LMBs, based on 2,5-diamino-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone, are successfully developed and tested for the first time. Validating critical factors for the design of organic battery electrode materials is expected to pave the way for advancing the development of high-efficiency and long cycle life solid-state organic batteries based on sulfides electrolytes.

Controlling Charge Transport in 2D Conductive MOFs─The Role of Nitrogen-Rich Ligands and Chemical Functionality.

Two-dimensional electrically conducting metal-organic frameworks (2D-e-MOFs) have emerged as a class of highly promising functional materials for a wide range of applications. However, despite the significant recent advances in 2D-e-MOFs, developing systems that can be postsynthetically chemically functionalized, while also allowing fine-tuning of the transport properties, remains challenging. Herein, we report two isostructural 2D-e-MOFs: Ni3(HITAT)2 and Ni3(HITBim)2 based on two new 3-fold symmetric ligands: 2,3,7,8,12,13-hexaaminotriazatruxene (HATAT) and 2,3,8,9,14,15-hexaaminotribenzimidazole (HATBim), respectively, with reactive sites for postfunctionalization. Ni3(HITAT)2 and Ni3(HITBim)2 exhibit temperature-activated charge transport, with bulk conductivity values of 44 and 0.5 mS cm-1, respectively. Density functional theory analysis attributes the difference to disparities in the electron density distribution within the parent ligands: nitrogen-rich HATBim exhibits localized electron density and a notably lower lowest unoccupied molecular orbital (LUMO) energy relative to HATAT. Precise amounts of methanesulfonyl groups are covalently bonded to the N-H indole moiety within the Ni3(HITAT)2 framework, modulating the electrical conductivity by a factor of ∼20. These results provide a blueprint for the design of porous functional materials with tunable chemical functionality and electrical response.

Bimetallic Anionic Organic Frameworks with Solid-State Cation Conduction for Charge Storage Applications.

A new phosphonate-based anionic bimetallic organic framework, with the general formula of A4 -Zn-DOBDP (wherein A is Li+ or Na+ , and DOBDP6- is the 2,5-dioxido-1,4-benzenediphosphate ligand) is prepared and characterized for energy storage applications. With four alkali cations per formula unit, the A4 -Zn-DOBDP MOF is found to be the first example of non-solvated cation conducting MOF with measured conductivities of 5.4×10-8  S cm-1 and 3.4×10-8  S cm-1 for Li4 - and Na4 - phases, indicating phase and composition effects of Li+ and Na+ shuttling through the channels. Three orders of magnitude increase in ionic conductivity is further attained upon solvation with propylene carbonate, placing this system among the best MOF ionic conductors at room temperature. As positive electrode material, Li4 -Zn-DOBDP delivers a specific capacity of 140 mAh g-1 at a high average discharge potential of 3.2 V (vs. Li+ /Li) with 90 % of capacity retention over 100 cycles. The significance of this research extends from the development of a new family of electroactive phosphonate-based MOFs with inherent ionic conductivity and reversible cation storage, to providing elementary insights into the development of highly sought yet still evasive MOFs with mixed-ion and electron conduction for energy storage applications.

Revealing the reversible solid-state electrochemistry of lithium-containing conjugated oximates for organic batteries.

In the rising advent of organic Li-ion positive electrode materials with increased energy content, chemistries with high redox potential and intrinsic oxidation stability remain a challenge. Here, we report the solid-phase reversible electrochemistry of the oximate organic redox functionality. The disclosed oximate chemistries, including cyclic, acyclic, aliphatic, and tetra-functional stereotypes, uncover the complex interplay between the molecular structure and the electroactivity. Among the exotic features, the most appealing one is the reversible electrochemical polymerization accompanying the charge storage process in solid phase, through intermolecular azodioxy bond coupling. The best-performing oximate delivers a high reversible capacity of 350 mAh g-1 at an average potential of 3.0 versus Li+/Li0, attaining 1 kWh kg-1 specific energy content at the material level metric. This work ascertains a strong link between electrochemistry, organic chemistry, and battery science by emphasizing on how different phases, mechanisms, and performances can be accessed using a single chemical functionality.

A tetranuclear cobalt(ii) phosphate possessing a D4R core: an efficient water oxidation catalyst.

The reaction of Co(OAc)2·4H2O with a sterically hindered phosphate ester, LH2, afforded a tetranuclear complex, [CoII(L)(CH3CN)]4·5CH3CN (1) [LH2 = 2,6-(diphenylmethyl)-4-isopropyl-phenyl phosphate]. The molecular structure of 1 reveals that it is a tetranuclear assembly where the Co(ii) centers are present in the alternate corners of a cube. The four Co(ii) centers are held together by four di-anionic [L]2- ligands. The fourth coordination site on Co(ii) is taken by an acetonitrile ligand. Changing the Co(ii) precursor from Co(OAc)2·4H2O to Co(NO3)2·6H2O afforded a mononuclear complex [CoII(LH)2(CH3CN)2(MeOH)2](MeOH)2 (2). In 2, the Co(ii) centre is surrounded by two monoanionic [LH]- ligands and a pair of methanol and acetonitrile solvents in a six-coordinate arrangement. 1 has been found to be an efficient catalyst for electrochemical water oxidation under highly basic conditions while the mononuclear analogue, 2, does not respond to electrochemical water oxidation. The tetranuclear catalyst has excellent electrochemical stability and longevity, as established by chronoamperometry and >1000 cycle durability tests under highly alkaline conditions. Excellent current densities of 1 and 10 mA cm-2 were achieved with overpotentials of 354 and 452 mV respectively. The turnover frequency of this catalyst was calculated to be 5.23 s-1 with an excellent faradaic efficiency of 97%, indicating the selective oxygen evolution reaction (OER) occurring with the aid of this catalyst. A mechanistic insight into the higher activity of complex 1 towards the OER compared to that of complex 2 is also provided using density functional theory based calculations.

On the hydrogen evolution reaction activity of graphene-hBN van der Waals heterostructures.

Although graphene technology has reached technology readiness level 9 and hydrogen fuel has been identified as a viable futuristic energy resource, pristine atomic layers such as graphene are found to be inactive towards the hydrogen evolution reaction (HER). Enhancing the intrinsic catalytic activity of a material and increasing its number of active sites by nanostructuring are two strategies in novel catalyst development. Here, electrocatalytically inert graphene (G) and hexagonal boron nitride (hBN) are made active for the HER by forming van der Waals (vdW) heterostructures via vertical stacking. The HER studies are conducted using defect free shear exfoliated graphite and hBN modified glassy carbon electrodes via layer by layer sequential stacking. The G/hBN stacking pattern (AA, AB, and AB') and stacking sequence (G/hBN or hBN/G) have been found to play important roles in the HER activity. Enhancement in the intrinsic activity of graphene by the formation of G/hBN vdW stacks has been further confirmed with thermally reduced graphene oxide and hBN based structures. Tunability in the HER performance of the G/hBN vdW stack is also confirmed via a three-dimensional rGO/hBN electrode. HER active sites in the G/hBN vdW structures are then mapped using density functional theory calculations, and an atomistic interpretation has been identified.

Stacking sequence dependent photo-electrocatalytic performance of CVD grown MoS2/graphene van der Waals solids.

New layered solids by the combinatorial stacking of different atomic layers are emanating as novel candidates for energy efficient devices. Here, sequentially stacked single layer graphene-molybdenum disulfide (MoS2) van der Waals (vdW) solids are demonstrated for their efficacy in the catalysis of hydrogen evolution reaction (HER), and importance of their stacking order in tuning the photo-electrocatalytic (PEC) efficiency is unraveled. Single layer graphene and a few layered MoS2 stacked vdW solids based transparent flexible electrodes were prepared, and a particular stacking sequence where top-graphene: bottom-MoS2/polydimethylsiloxane (PDMS) geometry (MSGR) exhibited the lowest onset and over potentials and a very high exchange current density (j 0 âˆ¼ 245 ± 1 µA cm-2) in acidic HER in comparison to the individual layers and other stacked configuration (MoS2 on top of graphene on PDMS, GRMS). The HER studies under dark and white light illuminations were conducted to explore the PEC responses of the devices. The augmented HER performance of MSGR is further confirmed from the charge transfer resistance measurements using electrochemical impedance spectroscopy. Role of graphene plasmonics and MoS2 to graphene electron transfer were studied, and this study unravels the importance of a new factor, stacking order of vdW layers, while designing novel devices from the layered solids.

Fluorographene based Ultrasensitive Ammonia Sensor.

Single molecule detection using graphene can be brought by tuning the interactions via specific dopants. Electrostatic interaction between the most electronegative element fluorine (F) and hydrogen (H) is one of the strong interactions in hydrogen bonding, and here we report the selective binding of ammonia/ammonium with F in fluorographene (FG) resulting to a change in the impedance of the system. Very low limit of detection value of ~0.44 pM with linearity over wide range of concentrations (1 pM-0.1 µM) is achieved using the FG based impedance sensor, andthisscreen printed FG sensor works in both ionized (ammonium) and un-ionized ammonia sensing platforms. The interaction energies of FG and NH3/NH4(+) are evaluated using density functional theory calculations and the interactions are mapped. Here FGs with two different amounts of fluorinecontents -~5 atomic% (C39H16F2) and ~24 atomic% (C39H16F12) - are theoretically and experimentally studied for selective, high sensitive and ultra-low level detection of ammonia. Fast responding, high sensitive, large area patternable FG based sensor platform demonstrated here can open new avenues for the development of point-of-care devices and clinical sensors.

Single step, bulk synthesis of engineered MoS2 quantum dots for multifunctional electrocatalysis.

Bi- or tri- functional catalysts based on atomic layers are receiving tremendous scientific attention due to their importance in various energy technologies. Recent studies on molybdenum disulphide (MoS2) nanosheets revealed that controlling the edge states and doping/modifying with suitable elements are highly important in tuning the catalytic activities of MoS2. Here we report a bulk, single step method to synthesize metal modified MoS2 quantum dots (QDs). Three elements, namely Fe, Mg and Li, are chosen to study the effects of dopants in the catalytic activities of MoS2. Fe and Mg are found to act like dopants in the MoS2 lattice forming respective doped MoS2 QDs, while Li formed an intercalated MoS2 QD. The efficacy and tunability of these luminescent doped QDs towards various electrocatalytic activities (hydrogen evolution reaction, oxygen evolution reaction and oxygen reduction action) are reported here.