Simultaneous Surface-Enhanced Raman Scattering with a Kerr Gate for Fluorescence Suppression.

The combination of surface-enhanced and Kerr-gated Raman spectroscopy for the enhancement of the Raman signal and suppression of fluorescence is reported. Surface-enhanced Raman scattering (SERS)-active gold substrates were demonstrated for the expansion of the surface generality of optical Kerr-gated Raman spectroscopy, broadening its applicability to the study of analytes that show a weak Raman signal in highly fluorescent media under (pre)resonant conditions. This approach is highlighted by the well-defined spectra of rhodamine 6G, Nile red, and Nile blue. The Raman spectra of fluorescent dyes were obtained only when SERS-active substrates were used in combination with the Kerr gate. To achieve enhancement of the weaker Raman scattering, Au films with different roughnesses or Au-core-shell-isolated nanoparticles (SHINs) were used. The use of SHINs enabled measurement of fluorescent dyes on non-SERS-active, optically flat Au, Cu, and Al substrates.

Lithium Insertion into Graphitic Carbon Observed via Operando Kerr-Gated Raman Spectroscopy Enables High State of Charge Diagnostics.

Monitoring the precise lithium inventory of the graphitic carbon electrode within the Li-ion battery, in order to assess cell aging, has remained challenging. Herein, operando electrochemical Kerr-gated Raman spectroscopy measurements on microcrystalline graphite during complete lithium insertion and extraction are reported and compared to conventional continuous-wave Raman microscopy. Suppression of the fluorescence emission signals via use of the Kerr gate enabled the measurement of the Raman graphitic bands of highly lithiated graphite where 0.5 ≤ x ≤ 1 for Li x C6. The broad graphitic band initially centered at ca. 1590 cm-1 for Li0.5C6 linearly shifted to ca. 1564 cm-1 with further lithiation to LiC6, thus offering a sensitive diagnostic tool to interrogate high states of charge of graphitic carbon-based negative electrodes.

A Pyrene-4,5,9,10-Tetraone-Based Covalent Organic Framework Delivers High Specific Capacity as a Li-Ion Positive Electrode.

Electrochemically active covalent organic frameworks (COFs) are promising electrode materials for Li-ion batteries. However, improving the specific capacities of COF-based electrodes requires materials with increased conductivity and a higher concentration of redox-active groups. Here, we designed a series of pyrene-4,5,9,10-tetraone COF (PT-COF) and carbon nanotube (CNT) composites (denoted as PT-COFX, where X = 10, 30, and 50 wt % of CNT) to address these challenges. Among the composites, PT-COF50 achieved a capacity of up to 280 mAh g-1 as normalized to the active COF material at a current density of 200 mA g-1, which is the highest capacity reported for a COF-based composite cathode electrode to date. Furthermore, PT-COF50 exhibited excellent rate performance, delivering a capacity of 229 mAh g-1 at 5000 mA g-1 (18.5C). Using operando Raman microscopy the reversible transformation of the redox-active carbonyl groups of PT-COF was determined, which rationalizes an overall 4 e-/4 Li+ redox process per pyrene-4,5,9,10-tetraone unit, accounting for its superior performance as a Li-ion battery electrode.

Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability.

Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium. We describe the lithium ultraphosphates Li3P5O14 and Li4P6O17 based on extended layers and chains of phosphate, respectively. Li3P5O14 presents a complex structure containing infinite ultraphosphate layers with 12-membered rings that are stacked alternately with lithium polyhedral layers. Two distinct vacant tetrahedral sites were identified at the end of two distinct finite Li6O1626- chains. Li4P6O17 features a new type of loop-branched chain defined by six PO43- tetrahedra. The ionic conductivities and electrochemical properties of Li3P5O14 were examined by impedance spectroscopy combined with DC polarization, NMR spectroscopy, and galvanostatic plating/stripping measurements. The structure of Li3P5O14 enables three-dimensional lithium migration that affords the highest ionic conductivity (8.5(5) × 10-7 S cm-1 at room temperature for bulk), comparable to that of commercialized LiPON glass thin film electrolytes, and lowest activation energy (0.43(7) eV) among all reported ternary Li-P-O phases. Both new lithium ultraphosphates are predicted to have high thermodynamic stability against oxidation, especially Li3P5O14, which is predicted to be stable to 4.8 V, significantly higher than that of LiPON and other solid electrolytes. The condensed phosphate units defining these ultraphosphate structures offer a new route to optimize the interplay of conductivity and electrochemical stability required, for example, in cathode coatings for lithium ion batteries.

Element selection for crystalline inorganic solid discovery guided by unsupervised machine learning of experimentally explored chemistry.

The selection of the elements to combine delimits the possible outcomes of synthetic chemistry because it determines the range of compositions and structures, and thus properties, that can arise. For example, in the solid state, the elemental components of a phase field will determine the likelihood of finding a new crystalline material. Researchers make these choices based on their understanding of chemical structure and bonding. Extensive data are available on those element combinations that produce synthetically isolable materials, but it is difficult to assimilate the scale of this information to guide selection from the diversity of potential new chemistries. Here, we show that unsupervised machine learning captures the complex patterns of similarity between element combinations that afford reported crystalline inorganic materials. This model guides prioritisation of quaternary phase fields containing two anions for synthetic exploration to identify lithium solid electrolytes in a collaborative workflow that leads to the discovery of Li3.3SnS3.3Cl0.7. The interstitial site occupancy combination in this defect stuffed wurtzite enables a low-barrier ion transport pathway in hexagonal close-packing.

Trapped interfacial redox introduces reversibility in the oxygen reduction reaction in a non-aqueous Ca2+ electrolyte.

Electrochemical investigations of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been conducted in a Ca2+-containing dimethyl sulfoxide electrolyte. While the ORR appears irreversible, the introduction of a tetrabutylammonium perchlorate (TBAClO4) co-salt in excess concentrations results in the gradual appearance of a quasi-reversible OER process. Combining the results of systematic cyclic voltammetry investigations, the degree of reversibility depends on the ion pair competition between Ca2+ and TBA+ cations to interact with generated superoxide (O2 -). When TBA+ is in larger concentrations, and large reductive overpotentials are applied, a quasi-reversible OER peak emerges with repeated cycling (characteristic of formulations without Ca2+ cations). In situ Raman microscopy and rotating ring-disc electrode (RRDE) experiments revealed more about the nature of species formed at the electrode surface and indicated the progressive evolution of a charge storage mechanism based upon trapped interfacial redox. The first electrochemical step involves generation of O2 -, followed primarily by partial passivation of the surface by Ca x O y product formation (the dominant initial reaction). Once this product matrix develops, the subsequent formation of TBA+--O2 - is contained within the Ca x O y product interlayer at the electrode surface and, consequently, undergoes a facile oxidation reaction to regenerate O2.

Crosslinked Polyimide and Reduced Graphene Oxide Composites as Long Cycle Life Positive Electrode for Lithium-Ion Cells.

Conjugated polymers with electrochemically active redox groups are a promising class of positive electrode material for lithium-ion batteries. However, most polymers, such as polyimides, possess low intrinsic conductivity, which results in low utilization of redox-active sites during charge cycling and, consequently, poor electrochemical performance. Here, it was shown that this limitation can be overcome by synthesizing polyimide composites (PIX) with reduced graphene oxide (rGO) using an in situ polycondensation reaction. The polyimide composites showed increased charge-transfer performance and much larger specific capacities, with PI50, which contains 50 wt % of rGO, showing the largest specific capacity of 172 mAh g-1 at 500 mA g-1 . This corresponds to a high utilization of the redox active sites in the active polyimide (86 %), and this composite retained 80 % of its initial capacity (125 mAh g-1 ) after 9000 cycles at 2000 mA g-1 .

Kerr gated Raman spectroscopy of LiPF6 salt and LiPF6-based organic carbonate electrolyte for Li-ion batteries.

Fluorescent species are formed during cycling of lithium ion batteries as a result of electrolyte decomposition due to the instability of the non-aqueous electrolytes and side reactions that occur at the electrode surface. The increase in the background fluorescence due to the presence of these components makes it harder to analyse data due to the spectroscopic overlap of Raman scattering and fluorescence. Herein, Kerr gated Raman spectroscopy was shown to be an effective technique for the isolation of the scattering effect from the fluorescence enabling the collection of the Raman spectra of LiPF6 salt and LiPF6-based organic carbonate electrolyte, without the interference of the fluorescence component. Kerr gated Raman was able to identify POF3 on the LiPF6 particle surface, after the addition of trace water.

Acyclic and Cyclic Alkyl and Ether-Functionalised Sulfonium Ionic Liquids Based on the [TFSI]- and [FSI]- Anions as Potential Electrolytes for Electrochemical Applications.

This work provides a study based on acyclic and cyclic sulfonium ionic liquids (ILs) with alkyl and ether-functionality on the cation paired with the bis{(trifluoromethyl)sulfonyl}imide, [TFSI]- , or the bis(fluorosulfonyl)imide, [FSI]- , as the counter anion. Herein, thermophysical characterisation of nine sulfonium-based ILs concerning the density, viscosity and conductivity and thermal properties including phase transition behaviour and decomposition temperature is reported. The electrochemical stability of the ILs was also measured by cyclic voltammetry at a glassy carbon macro-disk electrode. All of the ILs showed low melting point, low viscosity and good conductivity and could serve as potential electrolytes for energy storage devices.

Thermophysical and Electrochemical Properties of Ethereal Functionalised Cyclic Alkylammonium-based Ionic Liquids as Potential Electrolytes for Electrochemical Applications.

A series of hydrophobic room temperature ionic liquids (ILs) based on ethereal functionalised pyrrolidinium, piperidinium and azepanium cations bearing the bis[(trifluoromethyl)sulfonyl]imide, [TFSI]- , anion were synthesized and characterized. Their physicochemical properties such as density, viscosity and electrolytic conductivity, and thermal properties including phase transition behaviour and decomposition temperature have been measured. All of the ILs showed low melting point, low viscosity and good conductivity and the latter properties have been discussed in terms of the IL fragility, an important electrolyte feature of the transport properties of glass-forming ILs. Furthermore, the studied [TFSI]- -based ILs generally exhibit good electrochemical stabilities and, by coupling electrochemical experiments and DFT calculations, the effect of ether functionalisation at the IL cation on the electrochemical stability of the IL is discussed. Preliminary investigations into the Li-redox chemistry at a Cu working electrode are also reported as a function of ether-functionality within the pyrrolidinium-based IL family. Overall, the results show that these ionic liquids are suitable for electrochemical devices such as battery systems, fuel cells or supercapacitors.

Synthesis and Thermophysical Properties of Ether-Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications.

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis{(trifluoromethyl)sulfonyl}imide, [NTf2 ]- anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window, along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity, and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.

Effect of cation structure on the oxygen solubility and diffusivity in a range of bis{(trifluoromethyl)sulfonyl}imide anion based ionic liquids for lithium-air battery electrolytes.

This paper reports on the solubility and diffusivity of dissolved oxygen in a series of ionic liquids (ILs) based on the bis{(trifluoromethyl)sulfonyl}imide anion with a range of related alkyl and ether functionalised cyclic alkylammonium cations. Cyclic voltammetry has been used to observe the reduction of oxygen in ILs at a microdisk electrode and chronoamperometric measurements have then been applied to simultaneously determine both the concentration and the diffusion coefficient of oxygen in different ILs. The viscosity of the ILs and the calculated molar volume and free volume are also reported. It is found that, within this class of ILs, the oxygen diffusivity generally increases with decreasing viscosity of the neat IL. An inverse relationship between oxygen solubility and IL free volume is reported for the two IL families implying that oxygen is not simply occupying the available empty space. In addition, it is reported that the introduction of an ether-group into the IL cation structure promotes the diffusivity of dissolved oxygen but reduces the solubility of the gas.