Electrochemical Investigations of Sulfur-Decorated Organic Materials as Cathodes for Alkali Batteries.

Alkali metal-sulfur batteries (particularly, lithium/sodium- sulfur (Li/Na-S)) have attracted much attention because of their high energy density, the natural abundance of sulfur, and environmental friendliness. However, Li/Na-S batteries still face big challenges, such as limited cycle life, poor conductivity, large volume changes, and the "shuttle effect" caused by the high solubility of Li/Na-polysulfides. Herein, novel organosulfur-containing materials, i.e., bis(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)disulfide (BiTEMPS-OH) and 2,4-thiophene/arene copolymer (TAC) are proposed as cathode materials for Li and Na batteries. BiTEMPS-OH shows an initial discharge/charge capacity of 353/192 mAh g-1 and a capacity of 62 mAh g-1 after 200 cycles at 100 mA g-1 in ether-based Li-ion electrolyte. Meanwhile, TAC has an initial discharge/charge capacity of 270/248 mAh g-1 and better cycling performance (106 mAh g-1 after 200 cycles) than BiTEMPS-OH in the same electrolyte. However, the rate capability of TAC is limited by the slow diffusion of Li-ions. Both materials show inferior electrochemical performances in Na battery cells compared to the Li analogs. X-ray powder diffraction reveals that BiTEMPS-OH loses its crystalline structure permanently upon cycling in Li battery cells. X-ray photoelectron spectroscopy demonstrates the cleavage and partially reversible formation of S-S bonds in BiTEMPS-OH and the formation/decomposition of thick solid electrolyte interphase on the electrode surface of TAC.

Constructing Hollow Microcubes SnS2 as Negative Electrode for Sodium-ion and Potassium-ion Batteries.

Sodium/potassium-ion batteries (NIBs and KIBs) are considered the most promising candidates for lithium-ion batteries in energy storage fields. Tin sulfide (SnS2) is regarded as an attractive negative candidate for NIBs and KIBs thanks to its superior power density, high-rate performance and natural richness. Nevertheless, the slow dynamics, the enormous volume change and the decomposition of polysulfide intermediates limit its practical application. Herein, microcubes SnS2 were prepared through sacrificial MnCO3 template-assisted and a facile solvothermal reaction strategy and their performance was investigated in Na and K-based cells. The unique hollow cubic structure and well-confined SnS2 nanosheets play an important role in Na+/K+ rapid kinetic and alleviating volume change. The effect of the carbon additives (Super P/C65) on the electrochemical properties were investigated thoroughly. The in operando and ex-situ characterization provide a piece of direct evidence to clarify the storage mechanism of such conversion-alloying type negative electrode materials.

Electrochemical Investigation of Calcium Substituted Monoclinic Li3 V2 (PO4 )3 Negative Electrode Materials for Sodium- and Potassium-Ion Batteries.

Herein, the electrochemical properties and reaction mechanism of Li3-2 x Cax V2 (PO4 )3 /C (x = 0, 0.5, 1, and 1.5) as negative electrode materials for sodium-ion/potassium-ion batteries (SIBs/PIBs) are investigated. All samples undergo a mixed contribution of diffusion-controlled and pseudocapacitive-type processes in SIBs and PIBs via Trasatti Differentiation Method, while the latter increases with Ca content increase. Among them, Li3 V2 (PO4 )3 /C exhibits the highest reversible capacity in SIBs and PIBs, while Ca1.5 V2 (PO4 )3 /C shows the best rate performance with a capacity retention of 46% at 20 C in SIBs and 47% at 10 C in PIBs. This study demonstrates that the specific capacity of this type of material in SIBs and PIBs does not increase with the Ca-content as previously observed in lithium-ion system, but the stability and performance at a high C-rate can be improved by replacing Li+ with Ca2+ . This indicates that the insertion of different monovalent cations (Na+ /K+ ) can strongly influence the redox reaction and structure evolution of the host materials, due to the larger ion size of Na+ and K+ and their different kinetic properties with respect to Li+ . Furthermore, the working mechanism of both LVP/C and Ca1.5 V2 (PO4 )3 /C in SIBs are elucidated via in operando synchrotron diffraction and in operando X-ray absorption spectroscopy.

Study of the Lithium Storage Mechanism of N-Doped Carbon-Modified Cu2 S Electrodes for Lithium-Ion Batteries.

Owing to their high specific capacity and abundant reserve, Cux S compounds are promising electrode materials for lithium-ion batteries (LIBs). Carbon compositing could stabilize the Cux S structure and repress capacity fading during the electrochemical cycling, but the corresponding Li+ storage mechanism and stabilization effect should be further clarified. In this study, nanoscale Cu2 S was synthesized by CuS co-precipitation and thermal reduction with polyelectrolytes. High-temperature synchrotron radiation diffraction was used to monitor the thermal reduction process. During the first cycle, the conversion mechanism upon lithium storage in the Cu2 S/carbon was elucidated by operando synchrotron radiation diffraction and in situ X-ray absorption spectroscopy. The N-doped carbon-composited Cu2 S (Cu2 S/C) exhibits an initial discharge capacity of 425 mAh g-1 at 0.1 A g-1 , with a higher, long-term capacity of 523 mAh g-1 at 0.1 A g-1 after 200 cycles; in contrast, the bare CuS electrode exhibits 123 mAh g-1 after 200 cycles. Multiple-scan cyclic voltammetry proves that extra Li+ storage can mainly be ascribed to the contribution of the capacitive storage.

In Operando Synchrotron Diffraction and in Operando X-ray Absorption Spectroscopy Investigations of Orthorhombic V2O5 Nanowires as Cathode Materials for Mg-Ion Batteries.

Orthorhombic V2O5 nanowires were successfully synthesized via a hydrothermal method. A cell-configuration system was built utilizing V2O5 as the cathode and 1 M Mg(ClO4)2 electrolyte within acetonitrile, together with Mg xMo6S8 ( x ≈ 2) as the anode to investigate the structural evolution and oxidation state and local structural changes of V2O5. The V2O5 nanowires deliver an initial discharge/charge capacity of 103 mAh g-1/110 mAh g-1 and the highest discharge capacity of 130 mAh g-1 in the sixth cycle at C/20 rate in the cell-configuration system. In operando synchrotron diffraction and in operando X-ray absorption spectroscopy together with ex situ Raman and X-ray photoelectron spectroscopy reveal the reversibility of magnesium insertion/extraction and provide information on the crystal structure evolution and changes of the oxidation states during cycling.

Modification of Al Surface via Acidic Treatment and its Impact on Plating and Stripping.

Amorphous Al2 O3 film that naturally exists on any Al substrate is a critical bottleneck for the cyclic performance of metallic Al in rechargeable Al batteries. The so-called electron/ion insulator Al oxide slows down the anode's activation and hinders Al plating/stripping. The Al2 O3 film induces different surface properties (roughness and microstructure) on the metal. Al foils present two optically different sides (shiny and non-shiny), but their surface properties and influence on plating and stripping have not been studied so far. Compared to the shiny side, the non-shiny one has a higher (~28 %) surface roughness, and its greater concentration of active sites (for Al plating and stripping) yields higher current densities. Immersion pretreatments in Ionic-Liquid/AlCl3 -based electrolyte with various durations modify the surface properties of each side, forming an electrode-electrolyte interphase layer rich in Al, Cl, and N. The created interphase layer provides more tunneling paths for better Al diffusion upon plating and stripping. After 500 cycles, dendritic Al deposition, generated active sites, and the continuous removal of the Al metal and oxide cause accelerated local corrosion and electrode pulverization. We highlight the mechanical surface properties of cycled Al foil, considering the role of immersion pretreatment and the differences between the two sides.

Investigation of SnS2 -rGO Sandwich Structures as Negative Electrode for Sodium-Ion and Potassium-Ion Batteries.

Sodium-ion and potassium-ion batteries (NIBs and KIBs) are considered promising alternatives to replace lithium-ion batteries (LIBs) in energy storage applications due to the natural abundance and low cost of Na and K. Nevertheless, a critical challenge is that the large size of Na+ /K+ leads to a huge volume change of the hosting material during electrochemical cycling, resulting in rapid capacity decay. Among negative candidates for alkali-metal-ion batteries, SnS2 is attractive due to the competitively high specific capacity, low redox potential and high abundance. Porous few-layer SnS2 nanosheets are in situ grown on reduced graphene oxide, forming a SnS2 -rGO sandwich structure via strong C-O-Sn bonds. This nano-scaled sandwich structure not only shortens Na+ /K+ and electron transport pathways but also accommodates volume expansion, thereby enabling high and stable electrochemical cycling performance of SnS2 -rGO. This work explores the influence of different conductive carbons (Super P and C65) on the SnS2 -rGO electrode. In addition, the effects of the electrolyte additive fluoroethylene carbonate (FEC) on the electrochemical performance in NIBs and KIBs is evaluated. This work provides guidelines for optimized electrode structure design, electrolyte additives and carbon additives for the realization of better NIBs and KIBs.

Impact of Iodine Electrodeposition on Nanoporous Carbon Electrode Determined by EQCM, XPS and In Situ Raman Spectroscopy.

The charging of nanoporous carbon via electrodeposition of solid iodine from iodide-based electrolyte is an efficient and ecofriendly method to produce battery cathodes. Here, the interactions at the carbon/iodine interface from first contact with the aqueous electrolyte to the electrochemical polarization conditions in a hybrid cell are investigated by a combination of in situ and ex situ methods. EQCM investigations confirm the flushing out of water from the pores during iodine formation at the positive electrode. XPS of the carbon surface shows irreversible oxidation at the initial electrolyte immersion and to a larger extent during the first few charge/discharge cycles. This leads to the creation of functional groups at the surface while further reactive sites are consumed by iodine, causing a kind of passivation during a stable cycling regime. Two sources of carbon electrode structural modifications during iodine formation in the nanopores have been revealed by in situ Raman spectroscopy, (i) charge transfer and (ii) mechanical strain, both causing reversible changes and thus preventing performance deterioration during the long-term cycling of energy storage devices that use iodine-charged carbon electrodes.

Guest Ion-Dependent Reaction Mechanisms of New Pseudocapacitive Mg3 V4 (PO4 )6 /Carbon Composite as Negative Electrode for Monovalent-Ion Batteries.

Polyanion-type phosphate materials, such as M3 V2 (PO4 )3 (M = Li/Na/K), are promising as insertion-type negative electrodes for monovalent-ion batteries including Li/Na/K-ion batteries (lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs)) with fast charging/discharging and distinct redox peaks. However, it remains a great challenge to understand the reaction mechanism of materials upon monovalent-ion insertion. Here, triclinic Mg3 V4 (PO4 )6 /carbon composite (MgVP/C) with high thermal stability is synthesized via ball-milling and carbon-thermal reduction method and applied as a pseudocapacitive negative electrode in LIBs, SIBs, and PIBs. In operando and ex situ studies demonstrate the guest ion-dependent reaction mechanisms of MgVP/C upon monovalent-ion storage due to different sizes. MgVP/C undergoes an indirect conversion reaction to form Mg0 , V0 , and Li3 PO4 in LIBs, while in SIBs/PIBs the material only experiences a solid solution with the reduction of V3+ to V2+ . Moreover, in LIBs, MgVP/C delivers initial lithiation/delithiation capacities of 961/607 mAh g-1 (30/19 Li+ ions) for the first cycle, despite its low initial Coulombic efficiency, fast capacity decay for the first 200 cycles, and limited reversible insertion/deinsertion of 2 Na+ /K+ ions in SIBs/PIBs. This work reveals a new pseudocapacitive material and provides an advanced understanding of polyanion phosphate negative material for monovalent-ion batteries with guest ion-dependent energy storage mechanisms.

Advances in Nanomaterials for Lithium-Ion/Post-Lithium-Ion Batteries and Supercapacitors.

Energy storage and conversion are key factors for enabling the transition from fossil fuels to intermittent renewables [...].

Benefits of Organo-Aqueous Binary Solvents for Redox Supercapacitors Based on Polyoxometalates.

A novel redox electrolyte is proposed based on organo-aqueous solvent and a polyoxometalate (POM) redox moiety. The presence of dimethyl sulfoxide (DMSO) plays multiple roles in this system. Firstly, it enhances the cathodic electrochemical stability window by shifting the H2 evolution to lower potentials with respect to pure aqueous systems; secondly, it improves the reversibility of the redox reaction of the PW12O40 3- anion at low potentials. The presence of DMSO suppresses the Al corrosion, thus enabling the use of this metal as the current collector. An activated carbon-based supercapacitor is investigated in 1 M LiNO3/10 mM H3PW12O40 in a mixed DMSO/H2O solvent and compared with a POM-free electrolyte. In the presence of POMs, the device achieves better stability under floating conditions at 1.8 V. At 1 kW kg-1, it delivers a specific energy of 8 Wh kg-1 vs. 4.5 Wh kg-1 delivered from the POM-free device. The H2 evolution is further shifted by the POMs adsorbed on the activated carbon, which is one reason for the improved stability. The POM-containing cell demonstrates a mitigated self-discharge, owing to strong POMs adsorption into the carbon pores.

Effect of Continuous Capacity Rising Performed by FeS/Fe3 C/C Composite Electrodes for Lithium-Ion Batteries.

FeS-based composites are sustainable conversion electrode materials for lithium-ion batteries, combining features like low cost, environmental friendliness, and high capacities. However, they suffer from fast capacity decay and low electron conductivity. Herein, novel insights into a surprising phenomenon of this material are provided. A FeS/Fe3 C/C nanocomposite synthesized by a facile hydrothermal method is compared with pure FeS. When applied as anode materials for lithium-ion batteries, these two types of materials show different capacity evolution upon cycling. Surprisingly, the composite delivers a continuous increase in capacity instead of the expected capacity fading. This unique behavior is triggered by a catalyzing effect of Fe3 C nanoparticles. The Fe3 C phase is a beneficial byproduct of the synthesis and was not intentionally obtained. To further understand the effect of interconnected carbon balls on FeS-based electrodes, complementary analytic techniques are used. Ex situ X-ray radiation diffraction and ex situ scanning electron microscopy are employed to track phase fraction and morphology structure. In addition, the electrochemical kinetics and resistance are evaluated by cyclic voltammetry and electrochemical impedance spectroscopy. These results reveal that the interconnected carbon balls have a profound influence on the properties of FeS-based electrodes resulting in an increased electrode conductivity, reduced particle size, and maintenance of the structure integrity.

Elucidating the Mechanism of Li Insertion into Fe1-xS/Carbon via In Operando Synchrotron Studies.

The detailed understanding of kinetic and phase dynamics taking place in lithium-ion batteries (LIBs) is crucial for optimizing their properties. It was previously reported that Fe1-xS/C nanocomposites display a superior performance as anode materials in LIBs. However, the underlying lithium storage mechanism was not entirely understood during the 1st cycle. In this work, in operando synchrotron techniques are used to track lithium storage mechanisms during the 1st (de)-lithiation process in the Fe1-xS/C nanocomposite. The combination of in operando techniques enables the uncovering of the phase fraction alternations and crystal structural variations on different length-scales. Additionally, the investigation of kinetic processes, morphological changes, and internal resistance dynamics is discussed. These results reveal that the phase transition of Fe1-xS → Li2Fe1-xS2 → Fe0 + Li2S occurs during the 1st lithiation process. The redox reaction of Fe2+ + 2e- ⇌ Fe0 and the Fe K-edge X-ray absorption spectroscopy (XAS) transformation process are confirmed by in operando XAS. During the 1st de-lithiation process, Fe0 and Li2S convert to Li2-yFe1-xS2 and Li+ is extracted from Li2S to form Li2-yS. The phase transition from Li2S to Li2-yS is not detected in previous reports. After the 1st de-lithiation process, amorphous lithiated iron sulfide nanoparticles are embedded within the remaining Li2S matrix.

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

Immobilization of Polyiodide Redox Species in Porous Carbon for Battery-Like Electrodes in Eco-Friendly Hybrid Electrochemical Capacitors.

Hybrid electrochemical capacitors have emerged as attractive energy storage option, which perfectly fill the gap between electric double-layer capacitors (EDLCs) and batteries, combining in one device the high power of the former and the high energy of the latter. We show that the charging characteristics of the positive carbon electrode are transformed to behave like a battery operating at nearly constant potential after it is polarized in aqueous iodide electrolyte (1 mol L-1 NaI). Thermogravimetric analysis of the positive carbon electrode confirms the decomposition of iodides trapped inside the carbon pores in a wide temperature range from 190 °C to 425 °C, while Raman spectra of the positive electrode show characteristic peaks of I3- and I5- at 110 and 160 cm-1, respectively. After entrapment of polyiodides in the carbon pores by polarization in 1 mol L-1 NaI, the positive electrode retains the battery-like behavior in another cell, where it is coupled with a carbon-based negative electrode in aqueous NaNO3 electrolyte without any redox species. This new cell (the iodide-ion capacitor) demonstrates the charging characteristics of a hybrid capacitor with capacitance values comparable to the one using 1 mol L-1 NaI. The constant capacitance profile of the new hybrid cell in aqueous NaNO3 for 5000 galvanostatic charge/discharge cycles at 0.5 A g-1 shows that iodide species are confined to the positive battery-like electrode exhibiting negligible potential decay during self-discharge tests, and their shuttling to the negative electrode is prevented in this system.

Can Metallic Sodium Electrodes Affect the Electrochemistry of Sodium-Ion Batteries? Reactivity Issues and Perspectives.

Sodium-ion batteries (NIBs) are promising energy-storage devices with advantages such as low cost and highly abundant raw materials. To probe the electrochemical properties of NIBs, sodium metal is most frequently applied as the reference and/or counter electrode in state-of-the-art literature. However, the high reactivity of the sodium metal and its impact on the electrochemical performance is usually neglected. In this study, it is shown that spontaneous reactions of sodium metal with organic electrolytes and the importance of critical interpretation of electrochemical experiments is emphasized. When using sodium-metal half-cells, decomposition products contaminate the electrolyte during the electrochemical measurement and can easily lead to wrong conclusions about the stability of the active materials. The cycling stability is highly affected by these electrolyte contaminations, which is proven by comparing sodium-metal-free cell with sodium-metal-containing cells. Interestingly, a more stable cycling performance of the Li4 Ti5 O12 half-cells can be observed when replacing the Na metal counter and reference electrodes with activated carbon electrodes. This difference is attributed to the altered properties of the electrolyte as a result of contamination and to different surface chemistries.

Mechanism Study of Carbon Coating Effects on Conversion-Type Anode Materials in Lithium-Ion Batteries: Case Study of ZnMn2O4 and ZnO-MnO Composites.

The carbon coating strategy is intensively used in the modification of conversion-type anode materials to improve their cycling stability and rate capability. Thus, it is necessary to elucidate the modification mechanism induced by carbon coating. For this purpose, bare ZnMn2O4, carbon-derivative-coated ZnMn2O4, and carbon-coated ZnO-MnO composite materials have been synthesized and investigated in-depth. Herein, high-temperature synchrotron radiation diffraction is used to monitor the phase transition from ZnMn2O4 to ZnO-MnO composite during the carbonization process. The electrochemical performance has been evaluated by cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The carbon- and carbon-derivative-coated samples display well-improved cycling stability in terms of suppressed electrode polarization, a moderate increase in resistance, and slight capacity variation. The influence of carbon coating on the intrinsic conversion process is investigated by ex situ X-ray absorption spectroscopy, which reveals the evolution of Zn and Mn oxidation states. This result confirms that the strong capacity variation of the bare ZnMn2O4 is induced not only by the reversible charge storage in the solid electrolyte interphase but also by the phase evolution of active materials. Carbon coating is an effective method to prevent the additional oxidation of MnO to Mn3O4, which leads to a stabilization of the main conversion reaction.

Correlation of AC-impedance and in situ X-ray spectra of LiCoO2.

In-situ X-ray and AC-impedance spectra have been obtained simultaneously during the deintercalation of lithium from LiCoO2 using a specially designed electrochemical cell. The AC-dispersions have been correlated with the cell parameters obtained from the X-ray spectra. The correlation confirms previous hypothesis on the interpretation of the AC-dispersions in terms of an equivalent circuit comprising an element that relates the change of the intrinsic electronic conductivity, occurring at the early stages of deintercalation, to the semiconductor to metal transition caused by the change of the cell parameters.