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Manufacturers aim to commercialize efficient and safe batteries by finding new strategies. Solid-state electrolytes can be seen as an opportunity to develop batteries with a high energy density. They allow the use of lithium foil as the anode, increasing the energy density. Also, they are composed of nonflammable materials making them safer than liquid electrolytes. However, to enhance the electrochemical performances of forthcoming solid-state lithium metal batteries, phenomena governing ionic conductivity have yet to be mastered in such devices. Lithium isotopic tracing was successfully used in previous works to further understand lithium ion transport mechanisms in batteries. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and 6/7Li high-resolution solid-state nuclear magnetic resonance (ssNMR) spectroscopy are two complementary techniques probing local and global scale, respectively. Both techniques can distinguish lithium isotopes. Here, four polymer membranes were elaborated with the same lithium concentration, but with various isotopic enrichments from 7.6 to 95.4% of 6Li. The selected material was a poly(ethylene oxide) (PEO) membrane containing lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) as lithium salt. They are widely studied in the lithium battery field. First, reliable ToF-SIMS and ssNMR methodologies were validated in light of the converging results. They led to accurate determination of lithium isotopic abundance of polymer membranes with a 1 or a 2% uncertainty, respectively. Then, the developed methodologies were applied to characterize lithium self-diffusion in a polymer membrane. Furthermore, numerical simulations based on a two-dimensional diffusion model compared with ToF-SIMS analyses allowed us to extract a lithium self-diffusion coefficient of 1.6 × 10-12 m2·s-1 at 60 °C, which complements other published values. The robust methodologies described in this work can be extended to various applications and materials. They stand as powerful strategies to better understand lithium ionic transport, especially in multiphase materials, for example, in hybrid solid-state electrolytes.
RESUMEN
The introduction of lithiated components with different 7Li/6Li isotopic ratios, also called isotopic tracing, can give access to better understanding of lithium transport and lithiation processes in lithium-ion batteries. In this work, we propose a simple methodology based on high-resolution solid-state NMR for the determination of the 7Li/6Li ratio in silicon electrodes following different strategies of isotopic tracing. The 6Li and 7Li MAS NMR experiments allow obtaining resolved spectra whose spectral components can be assigned to different moieties of the materials. In order to measure the ratio of the 6Li/7Li NMR integrals, a silicon electrode with a natural 7Li/6Li isotope abundance was used as a reference. This calibration can then be used to determine the 7Li/6Li ratio of any similar samples. This method was applied to study the phenomena occurring at the interface between a silicon electrode and a labeled electrolyte, which is an essential step for isotopic tracing experiments in systems after the formation of the solid electrolyte interphase (SEI). Beyond the isotopic exchanges between the SEI and the electrolyte already observed in the literature, our results show that isotopic exchanges also involve Li-Si alloys in the electrode bulk. Within a 52-hour contact, the electrolyte labeling disappeared: isotopic concentrations of the electrolyte and electrode become practically homogenized. However, at the electrode level, different silicides are characterized by rather different isotopic enrichment. In the present work, ToF SIMS and liquid state NMR were also used to cross-check and discuss the solid-state NMR method we have proposed.
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Carbon coatings can help to stabilize the electrochemical performance of high-energy anodes using silicon nanoparticles as the active material. In this work, the comparison of the behavior and chemical composition of the Solid Electrolyte Interphase (SEI) was carried out between Si nanoparticles and carbon-coated Si nanoparticles (Si@C). A combination of two complementary analytical techniques, Electrochemical Impedance Spectroscopy and X-ray Photoelectron Spectroscopy (XPS), was used to determine the intrinsic characteristics of the SEI. It was demonstrated that the SEI on Si particles is more resistive than the SEI on the Si@C particles. XPS demonstrated that the interface on the Si particles contains more oxygen when not covered with carbon, which shows that a protective layer of carbon helps to reduce the number of inorganic components, leading to more resistive SEI. The combination of those two analytical techniques is implemented to highlight the features and evolution of interfaces in different battery technologies.
RESUMEN
Failure mechanisms associated with silicon-based anodes are limiting the implementation of high-capacity lithium-ion batteries. Understanding the aging mechanism that deteriorates the anode performance and introducing novel-architectured composites offer new possibilities for improving the functionality of the electrodes. Here, the characterization of nano-architectured composite anode composed of active amorphous silicon domains (a-Si, 20 nm) and crystalline iron disilicide (c-FeSi2 , 5-15 nm) alloyed particles dispersed in a graphite matrix is reported. This unique hierarchical architecture yields long-term mechanical, structural, and cycling stability. Using advanced electron microscopy techniques, the nanoscale morphology and chemical evolution of the active particles upon lithiation/delithiation are investigated. Due to the volumetric variations of Si during lithiation/delithiation, the morphology of the a-Si/c-FeSi2 alloy evolves from a core-shell to a tree-branch type structure, wherein the continuous network of the active a-Si remains intact yielding capacity retention of 70% after 700 cycles. The root cause of electrode polarization, initial capacity fading, and electrode swelling is discussed and has profound implications for the development of stable lithium-ion batteries.
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The understanding of the phenomena occurring during immersion of LiNi0.5Mn0.3Co0.2O2 (NMC) in water is helpful to devise new strategies toward the implementation of aqueous processing of this high-capacity cathode material. Immersion of NMC powder in water leads to both structural modification of the particles surface as observed by high-resolution scanning transmission electron microscopy and the formation of lithium-based compounds over the surface (LiOH, Li2CO3) in greater amount than after long-time exposure to ambient air, as confirmed by pH titration and 7Li MAS NMR analysis. The surface compounds adversely affect the electrochemical performance and are notably responsible for the alkaline pH of the aqueous slurry, which causes corrosion of the aluminum collector during coating of the electrode. The corrosion is avoided by adding phosphoric acid to the slurry as it lowers the pH, and it also enhances the cycling stability of the water-based electrodes due to the phosphate compounds formed at the particles surface, as evidenced by X-ray photoelectron spectroscopy analysis.
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The sustainability through the energy and environmental costs involve the development of new cathode materials, considering the material abundance, the toxicity, and the end of life. Currently, some synthesis methods of new cathode materials and a large majority of recycling processes are based on the use of acidic solutions. This study addresses the mechanistic and limiting aspects on the dissolution of the layered LiNi1/3Mn1/3Co1/3O2 oxide in acidic solution. The results show a dissolution of the active cathode material in two steps, which leads to the formation of a well-defined core-shell structure inducing an enrichment in manganese on the particle surface. The crucial role of lithium extraction is discussed and considered as the source of a "self-regulating" dissolution process. The delithiation involves a cumulative charge compensation by the cationic and anionic redox reactions. The electrons generated from the compensation of charge conduct to the dissolution by the protons. The delithiation and its implications on the side reactions, by the modification of the potential, explain the structural and compositional evolutions observed toward a composite material MnO2·Li xMO2 (M = Ni, Mn, and Co). The study shows a clear way to produce new cathode materials and recover transition metals from Li-ion batteries by hydrometallurgical processes.
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Silicon is a serious candidate to replace graphite in electrodes because it offers a specific capacity almost 10 times higher than that of carbonaceous materials. However, cycling performances of Si electrodes remain very limited because of the huge volume changes upon alloying and dealloying with lithium. A fine understanding of the lithiation mechanism of silicon electrodes will help to design more robust architectures. In this work, an amorphous silicon thin film has been used as a model for a better understanding of lithiation mechanism. Lithium distribution in the Si layer has been thoroughly investigated by coupling powerful characterization tools: X-ray photoelectron spectroscopy (XPS) and secondary-ion mass spectrometry (ToF-SIMS). In particular, cross-analysis of different lithiation states has been carried out. A lithiation front moving forward over the state of charge has been highlighted. The quantification of the LixSi alloy indicates a lithium amount much higher than that of the Li/Si ratio estimated in previous studies. This anomaly leads to a description of the lithiation mechanism based on the presence of fast diffusion paths for Li throughout the Si layer. These paths would be a second driving force for silicon alloying and lithium segregation at the collector interface. SEM observations of a FIB cut corroborate this mechanism.
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Carbon-covered silicon nanoparticles (Si@C) were synthesized for the first time by a one-step continuous process in a novel two stages laser pyrolysis reactor. Crystallized silicon cores formed in a first stage were covered in the second stage by a continuous shell mainly consisting in low organized sp(2) carbon. At the Si/C interface silicon carbide is absent. Moreover, the presence of silicon oxide is reduced compared to materials synthesized in several steps, allowing the use of such material as promising anode material in lithium-ion batteries (LIB). Auger Electron Spectroscopy (AES) analysis of the samples at both SiKLL and SiLVV edges proved the uniformity of the carbon coating. Cyclic voltammetry was used to compare the stability of Si and Si@C active materials. In half-cell configuration, Si@C exhibits a high and stable capacity of 2400 mAh g(-1) at C/10 and up to 500 mAh g(-1) over 500 cycles at 2C. The retention of the capacity is attributed to the protective effect of the carbon shell, which avoids direct contact between the silicon surface and the electrolyte.
RESUMEN
With a specific capacity of 3600 mA h g(-1), silicon is a promising anode active material for Li-ion batteries (LIBs). However, because of the huge volume changes undergone by Si particles upon (de)alloying with lithium, Si electrodes suffer from rapid capacity fading. A deep understanding of the associated failure mechanisms is necessary to improve these electrochemical performances. To reach this goal, we investigate here nano-Si based electrodes by several characterization techniques. Thanks to all these techniques, many aspects, such as the behaviour of the active material or the solid electrolyte interphase (SEI) and the lithiation mechanisms, are studied upon cycling. A clear picture of the failure mechanisms of nano-Si based electrodes is provided. In particular, by combining Hg analyses, SEM observations of electrode cross-sections, and EIS measurements, we follow the evolution of the porosity within the electrode. For the first time, our results clearly show a real dynamic of the pore size distribution: the first cycles lead to the formation of a micrometric porosity which is not present initially. During the following cycles, these large pores are progressively filled up with SEI products which form continuously at the Si particle surface. Thus, from the 50th cycle, Li(+) ion diffusion is dramatically hindered leading to a strongly heterogeneous lithiation of the electrode and a rapid capacity fading.
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Binary mixtures of cyclic (TMS) or acyclic sulfones (MIS, EIS and EMS) with EMC or DMC have been used in electrolytes containing LiPF6 (1 M) in both Li4Ti5O12/Li half-cells and Li4+xTi5O12/Li4Ti5O12 symmetric cells and compared with standard EC/EMC or EC/DMC mixtures. In half-cells, sulfone-based electrolytes cannot be satisfactorily cycled owing to the formation of a resistive layer at the lithium interface, which is not stable and generates species (RSO2(-) and RSO3(-)) able to migrate toward the titanate electrode interface. Potentiostatic and galvanostatic tests of Li4Ti5O12/Li half-cells show that charge transfer resistance increases drastically when sulfones are used in the electrolyte composition. Moreover, cyclability and coulombic efficiency are low. Conversely, when symmetric Li4+xTi5O12/Li4Ti5O12 cells are used, it is demonstrated that MIS-(methyl isopropyl sulfone) and TMS-(tetra methyl sulfone) based electrolytes exhibit reasonable electrochemical performances as compared to the EC/DMC or EC/EMC standard mixtures. Surface analysis by XPS of both the Li4+xTi5O12 (partially oxidized) and Li7Ti5O12 (reduced) electrodes taken from symmetric cells reveals that sulfones do not participate in the formation of surface layers. Alkylcarbonates (EMC or DMC), used as co-solvents in sulfone-based binary electrolytes, ensure the formation of surface layers at the titanate interfaces. Therefore, EMC reduction at the two Li4+xTi5O12/electrolyte interfaces in symmetric cells leads to the formation of carbonates, ethers and mineral compounds such as ROCO2Li and Li2CO3. Finally, huge amounts of LiF are detected at the titanate electrode surface, resulting in an increase in the resistivity of symmetric cells and capacity losses.
RESUMEN
Cycling after storage of LiNi0.4Mn1.6O4/Li4Ti5O12 cells evidences lower total capacity losses for EMS-, TMS- and MIS-based electrolytes as compared to EC-based at 20 °C. The shuttle-type mechanism induced by the electrolyte oxidation is mainly present in the accumulators at this temperature, as compared to those due to the Mn(2+) and Ni(2+) dissolution. At 30 and 40 °C, EC is responsible for the polymer film formation on the LiNi0.4Mn1.6O4 surface, which limits the transition metal ion dissolution. This results in lower reversible capacity losses compared to sulfones, but are still important: 45% at 30 °C and 70-75% at 40 °C. XPS spectra reveal that EMS does not contribute to the surface film formation on the LiNi0.4Mn1.6O4 spinel, regardless of the cycling conditions and temperature. Only the EMC decomposition at high potential in sulfone/EMC electrolytes is responsible for an organic layer formation, which is composed of low passivating oligomers that comprise the C-O and C=O functional groups. Sulfones are promising compounds to be used in high voltage Li-ion batteries thanks to their non-reactivity towards the LiNi0.4Mn1.6O4 cathode. However, this does not allow the deposition of surface films that would have enabled stopping the Mn(2+) and Ni(2+) dissolution in the electrolyte. This is responsible for degraded performances of LiNi0.4Mn1.6O4/Li4Ti5O12 cells as compared to EC-based electrolytes over ambient temperatures, especially at 30 °C.
RESUMEN
Organic thin-film transistor (OTFT) performance depends on the chemical characteristics of the interface between functional semiconductor/dielectric/conductor materials. Here we report for the first time that OTFT response in top-gate architectures strongly depends on the substrate chemical functionalization. Depending on the nature of the substrate surface, dramatic variations and opposite trends of the TFT threshold voltage (~±50 V) and OFF current (10(5)×!) are observed for both p- and n-channel semiconductors. However, the field-effect mobility varies only marginally (~2×). Our results demonstrate that the substrate is not a mere passive mechanical support.