The (electro)chemical reactions between positive electrodes and electrolytes are not well understood. We examined the oxidation of a LiPF6-based electrolyte with ethylene carbonate (EC) with layered ...lithium nickel, manganese, and cobalt oxides (NMC). Density functional theory calculations showed that the driving force for EC dehydrogenation on oxides, yielding surface protic species, increased with greater Ni content in NMC. Ex situ infrared and Raman spectroscopy revealed experimental evidence for EC dehydrogenation on charged NMC surfaces. Protic species on charged NMC surfaces from EC dehydrogenation could further react with LiPF6 to generate less-coordinated F species such as PF3O-like and lithium nickel oxyfluoride species on charged NMC particles and HF and PF2O2 – in the electrolyte. Larger degree of salt decomposition was coupled with increasing EC dehydrogenation on charged NMC with increasing Ni or lithium deintercalation. An oxide-mediated chemical oxidation of electrolytes was proposed, providing new insights in stabilizing high-energy positive electrodes and improving Li-ion battery cycle life.
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A Si-based anode with improved performance can be achieved using high-energy ball-milling as a cheap and easy process to produce Si powders prepared from a coarse-grained material. Ball-milled ...powders present all the advantages of nanometric Si powders, but not the drawbacks. Milled powders are nanostructured with micrometric agglomerates (median size similar to 10 mu m), made of submicrometric cold-welded particles with a crystallite size of similar to 10 nm. The micrometric particle size provides handling and non-toxicity advantages compared to nanometric powders, as well as four times higher tap density. The nanostructuration is assumed to provide a shortened Li super(+) diffusion path, a fast Li super(+) diffusion path along grain boundaries and a smoother phase transition upon cycling. Compared to non-milled 1-5 mu m powders, the improved performance of nanostructured milled Si powders is linked to a strong lowering of particle disconnection at each charge, while the irreversibility due to SEI formation remains unchanged. An electrode prepared in acidic conditions with the CMC binder achieves 600 cycles at more than 1170 mA h per gram of the milled Si-based electrode, in an electrolyte containing FEC/VC SEI-forming additives, with a coulombic efficiency above 99%, compared to less than 100 cycles at the same capacity for an electrode containing nanometric Si powder.
Achieving the full potential of magnesium-ion batteries (MIBs) is still a challenge due to the lack of adequate electrodes or electrolytes. Grignard-based electrolytes show excellent Mg ...plating/stripping, but their incompatibility with oxide cathodes restricts their use. Conventional electrolytes like bis(trifluoromethanesulfonyl)imide ((Mg(TFSI)2) solutions are incompatible with Mg metal, which hinders their application in high-energy Mg batteries. In this regard, alloys can be game changers. The insertion/extraction of Mg2+ in alloys is possible in conventional electrolytes, suggesting the absence of a passivation layer or the formation of a conductive surface layer. Yet, the role and influence of this layer on the alloys performance have been studied only scarcely. To evaluate the reactivity of alloys, we studied InSb as a model material. Ex situ X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy were used to investigate the surface behavior of InSb in both Grignard and conventional Mg(TFSI)2/DME electrolytes. For the Grignard electrolyte, we discovered an intrinsic instability of both solvent and salt against InSb. XPS showed the formation of a thick surface layer consisting of hydrocarbon species and degradation products from the solvent (THF) and salt (C2H5MgCl−(C2H5)2AlCl). On the contrary, this study highlighted the stability of InSb in Mg(TFSI)2 electrolyte.
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Fundamental understanding of the reactivity between electrode and electrolyte is key to design the safety and life of Li-ion batteries. Herein X-ray photoelectron spectroscopy was used to examine the ...electrode/electrolyte interface (EEI) on carbon-free, binder-free LiCoO2 powder and thin-film electrodes in LP57 electrolyte as function of potential. Upon charging of LiCoO2 a marked growth of oxygenated and carbonated species was observed on the surface, consistent with electrolyte oxidation at high potentials. We also demonstrated that LiCoO2 oxide surface was prone to decompose the salt starting at 4.1 VLi, as evidenced by the increase of LiF and LixPFyOz species upon charging. By DFT calculations we proposed a correlation between the interface composition and the thermodynamic tendency of the EC solvent for dissociative adsorption on the LixCoO2 surface, through the generation of reactive acidic OH groups on the oxide surface, which can have a role in the observed salt decomposition. This is consistent with the evidence of HF and PF2O2− species at 4.6 VLi observed by solution 19F-NMR measurements. Finally we compared EEI composition between composite and model electrodes and discussed the changes and mechanisms induced by the electrode composition or the use of electrolyte additives. We showed that the addition of diphenyl carbonate (DPC) in the electrolyte has a strong impact on the formation of solvent and salt decomposition products at the EEI layer.
Anion redox in lithium transition-metal oxides such as Li2RuO3 and Li2MnO3 has catalyzed intensive research efforts to find transition-metal oxides with anion redox that may boost the energy density ...of lithium-ion batteries. The physical origin of the observed anion redox remains debatable, and more direct experimental evidence is needed. In this work, we have shown electronic signatures of oxygen–oxygen coupling, direct evidence central to lattice oxygen redox (O2–/(O2) n−), in charged Li2–x RuO3 after Ru oxidation (Ru4+/Ru5+) upon first electron removal with lithium deintercalation. Experimental Ru L3-edge high-energy-resolution fluorescence-detected X-ray absorption spectra (HERFD-XAS), supported by ab initio simulations, revealed that the increased intensity in the high-energy shoulder upon lithium deintercalation resulted from increased O–O coupling, inducing (O–O) σ*-like states with π overlap with Ru d-manifolds, in agreement with O K-edge XAS spectra. Experimental and simulated O K-edge X-ray emission spectra further supported this observation with the broadening of the oxygen nonbonding feature upon charging, also originated from (O–O) σ* states. This lattice oxygen redox of Li2–x RuO3 was accompanied by a small amount of O2 evolution in the first charge from differential electrochemistry mass spectrometry but diminished in the subsequent cycles, in agreement with the more reduced states of Ru in later cycles from Ru L3-edge HERFD-XAS. These observations indicated that Ru redox contributed more to discharge capacities after the first cycle. This study has pinpointed the key spectral fingerprints related to lattice oxygen redox from a molecular level and constructed a transferrable framework to rationally interpret the spectroscopic features by combining advanced experiments and theoretical calculations to design materials for Li-ion batteries and electrocatalysis applications.
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An electrochemically roughened copper foil was evaluated as a current collector for micrometric Si powder (ball-milled) based electrodes prepared by the conventional slurry-coating method. The ...formation of a bunch of copper nanowires on the current collector provides a rough surface, which enhances the adhesion of the Si composite electrode as confirmed from scratch tests. This produces a major decrease of the irreversible capacity associated with the electrical disconnection of the Si particles with cycling, which results in a great improvement of the electrode cycle life. With such a roughened Cu current collector, the micrometric Si-based electrode is able to maintain a discharge capacity of 1200mAhg−1 for at least 1000 cycles.
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•Si-based anodes with electrochemically roughened current collector were studied.•The Cu nanowires on the current collector enhance the adhesion of the Si coating.•This limits the electrical disconnection of the Si particles with cycling.•This results in an great improvement of the electrode cycle life.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Lithium–air (O2) batteries have shown great promise because of their high gravimetric energy densityan order of magnitude greater than Li-ionbut challenges such as electrolyte and electrode ...instability have led to poor capacity retention and low cycle life. Positive electrodes such as carbon and inorganic metal oxides have been heavily explored, but the degradation of carbon and the limited surface area of the metal oxides limit their practical use. In this work, we study the electron-conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and show it can support oxygen reduction to form Li2O2 in a nonaqueous environment. We also propose a degradation mechanism and show that the formation of sulfone functionalities on the PEDOT surface and cleavage of the polymer repeat unit impairs electron conductivity and leads to poor cycling. Our findings are important in the search for new Li–O2 electrodes, and the physical insights provided are significant and timely.
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Development of better energy storage media is vital in the adoption of renewable energy technologies, and lithium–air (O2) batteries have spurred great interest. However, current Li–O2 batteries are ...plagued by unwanted side reactions, flammable electrolytes, and slow kinetics attributed to the 2 mol e–/mol O2 peroxide chemistry. In this work, we show that a gel polymer electrolyte consisting of a polymer, ionic liquid, and salt can control the oxygen reduction chemistry in a Li–O2 cell (switching from a 2 e– to a 1 e– superoxide chemistry), support the formation of ionic liquid–superoxide complexes, and reduce the number of reactive species present in the cell. A one electron process could allow for newer energy-dense Li–O2 batteries with faster kinetics and higher energy efficiencies typical of superoxide-dominant Na–O2 and K–O2 batteries.
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Li-air batteries possess higher specific energies than the current Li-ion batteries. Major drawbacks of the air cathode include the sluggish kinetics of the oxygen reduction (OER), high ...overpotentials and pore clogging during discharge processes. Metal–Organic Frameworks (MOFs) appear as promising materials because of their high surface areas, tailorable pore sizes and catalytic centers. In this work, we propose to use, for the first time, aluminum terephthalate (well known as MIL-53) as a flexible air cathode for Li-O2 batteries. This compound was synthetized through hydrothermal and microwave-assisted routes, leading to different particle sizes with different aspect ratios. The electrochemical properties of both materials seem to be equivalent. Several behaviors are observed depending on the initial value of the first discharge capacity. When the first discharge capacity is higher, no OER occurs, leading to a fast decrease in the capacity during cycling. The nature and the morphology of the discharge products are investigated using ex situ analysis (XRD, SEM and XPS). For both MIL-53 materials, lithium peroxide Li2O2 is found as the main discharge product. A morphological evolution of the Li2O2 particles occurs upon cycling (stacked thin plates, toroids or pseudo-spheres).
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A multi‐tetrazine compound tailored for grafting on graphene sheets has been designed and investigated. It is composed of hydrogen substituted tetrazines involved in inverse Diels‐Alder demand ...cycloaddition reactions for grafting and a central dialkoxytetrazine to confer redox properties to the final material. The successful incorporation of this compound in reduced graphene oxide was demonstrated by elemental analysis, XPS, Raman spectroscopy, AFM, SEM and XRD. Cyclic voltammetry shows the redox activity of the remaining central tetrazine unit in graphene and allows to assess the specific capacity of the material. A significant increase in the specific capacity was found compared to pristine graphene and another tetrazine model compound bearing only one grafting unit. This result was assigned to an increase in the specific area in relation to bridges created between graphene sheets, as evidenced by AFM and XRD. The performance in energy storage were assessed in symmetrical Swagelok cells confirming the high impact of the functionalization on capacitance values.
Supercapacitors: Functionalization of reduced graphene oxide sheets by redox‐active bridging units leading to an enhanced capacitance and energy storage ability.
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