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Aluminum (Al) is one of the most promising active materials for producing next-generation negative electrodes for lithium (Li)-ion batteries. It features low density, high specific capacity, and low working potential, making it ideal for producing energy-dense cells. However, this material loses its electrochemical activity within 100 cycles, making it practically unusable. Several claims in the literature support the idea that a dual degradation mechanism is at play. Firstly, the slow diffusion of Li in the Al matrix causes the electrochemical reactions to be partly irreversible, making the initial capacity of the cell drop. Second, the stresses caused by cycling make the active material pulverize and lose activity. Recent work shows that shortening the diffusion path of Li by 3D structuring is an effective way to mitigate the first capacity loss mechanism, while alloying Al with other elements effectively mitigates the second one. In this work, we demonstrate that the benefits of 3D structuring and alloying are cumulative and that a mesh made of an Al-magnesium alloy performs better than both a pure Al foil and a foil of an Al-Mg alloy.
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Recently, the formation of the ceramic-ionic liquid composite has attracted huge interest in the scientific community. In this work, we investigated the chemical reactions occurring between NASICON LAGP ceramic electrolyte and ionic liquid pyr13TFSI. This study allowed us to identify the cation exchange reaction pyr13-Li occurring on the LAGP surface, forming a LiTFSI salt that was detected by the nuclear magnetic resonance analysis. In addition, using 6Li foils, we succeeded in demonstrating that both LAGP and LiTFSI:pyr13TFSI participate in the diffusion of Li ions by the formation of an ionic bridge between two species.
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Líquidos Iónicos , Cationes , Electrólitos , LitioRESUMEN
We present the first results of in situ scanning electron microscopy (SEM) of an all-solid Li battery with a nickel-manganese-cobalt-oxide (NMC-622) cathode at 50 °C and an operating voltage of 2.7-4.3 V. Experiments were conducted under a constant current at several C rates (nC rate: cycling in 1/n h): C/12, C/6, and C/3. The microstructure evolution during cycling was monitored by continuous secondary electron imaging. We found that the chemical degradation of the solid polymer electrolyte (SPE) was the main mechanism for battery failure. This degradation was observed in the form of a gradual thinning of the SPE as a function of cycling time, resulting in gas generation from the cell. We also present various dynamic electrochemical and mechanical phenomena, as observed by SEM images, and compare the performance of this battery with that of an all-solid Li battery with a LiFePO4 cathode.
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Li metal batteries suffer from dendrite formation which causes short circuit of the battery. Therefore, it is important to understand the chemical composition and growth mechanism of dendrites that limit battery efficiency and cycle life. In this study, in situ scanning electron microscopy was employed to monitor the cycling behavior of all-solid Li metal batteries with LiFePO4 cathodes. Chemical analyses of the dendrites were conducted using a windowless energy dispersive spectroscopy detector, which showed that the dendrites are not metallic lithium as universally recognized. Our results revealed the carbide nature of the dendrites with a hollow morphology and hardness greater than that of pure lithium. These carbide-based dendrites were able to perforate through the polymer, which was confirmed by milling the polymer using focused ion beam. It was also shown that applying pressure on the battery can suppress growth of the dendrites.
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One of the main challenges in improving fast charging lithium-ion batteries is the development of suitable active materials for cathodes and anodes. Many materials suffer from unacceptable structural changes under high currents and/or low intrinsic conductivities. Experimental measurements are required to optimize these properties, but few techniques are able to spatially resolve ionic transport properties at small length scales. Here we demonstrate an atomic force microscope (AFM)-based technique to measure local ionic transport on LiFePO4 to correlate with the structural and compositional analysis of the same region. By comparing the measured values with density functional theory (DFT) calculations, we demonstrate that Coulomb interactions between ions give rise to a collective activation energy for ionic transport that is dominated by large phase boundary hopping barriers. We successfully measure both the collective activation energy and the smaller single-ion bulk hopping barrier and obtain excellent agreement with values obtained from our DFT calculations.
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Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.
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Calcio/química , Hierro/química , Compuestos de Litio/química , Nanopartículas/química , Fosfatos/química , Nanopartículas/ultraestructura , Propiedades de SuperficieRESUMEN
In phospho-olivine type structures with mixed cations (LiM1M2PO4), the octahedral M1 and M2 sites that dictate the degree of intersites order/disorder play a key role in determining their electrochemical redox potentials. In the case of LiFexMn1-xPO4, for example, in micrometer-sized particles synthesized via hydrothermal route, two separate redox centers corresponding to Fe(2+)/Fe(3+) (3.5 V vs Li/Li(+)) and Mn(2+)/Mn(3+) (4.1 V vs Li/Li(+)), due to the collective Mn-O-Fe interactions in the olivine lattice, are commonly observed in the electrochemical measurements. These two redox processes are directly reflected as two distinct peak potentials in cyclic voltammetry (CV) and equivalently as two voltage plateaus in their standard charge/discharge characteristics (in Li ion batteries). On the contrary, we observed a single broad peak in CV from LiFe0.5Mn0.5PO4 platelet-shaped (â¼10 nm thick) nanocrystals that we are reporting in this work. Structural and compositional analysis showed that in these nanoplatelets the cations (Fe, Mn) are rather homogeneously distributed in the lattice, which is apparently the reason for a synergetic effect on the redox potentials, in contrast to LiFe0.5Mn0.5PO4 samples obtained via hydrothermal routes. After a typical carbon-coating process in a reducing atmosphere (Ar/H2), these LiFe0.5Mn0.5PO4 nanoplatelets undergo a rearrangement of their cations into Mn-rich and Fe-rich domains. Only after such cation rearrangement (via segregation) in the nanocrystals, the redox processes evolved at two distinct potentials, corresponding to the standard Fe(2+)/Fe(3+) and Mn(2+)/Mn(3+) redox centers. Our experimental findings provide new insight into mixed-cation olivine structures in which the degree of cations mixing in the olivine lattice directly influences the redox potentials, which in turn determine their charge/discharge characteristics.
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Técnicas Electroquímicas , Metales/química , Nanopartículas/química , Fosfatos/química , Nanopartículas/ultraestructura , Oxidación-ReducciónRESUMEN
LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently "plagued" by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of â¼ 155 mAh/g, â¼ 135 mAh/g, and â¼ 125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of â¼ 70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was â¼ 30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries.
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Nowadays, solid electrolytes are considered the main alternative to conventional liquid electrolytes in lithium batteries. The fabrication of these materials is however limited by the strict synthesis conditions, requiring high temperatures which can negatively impact the final performances. Here, it is shown that a modification of garnet-based Li7 La3 Zr2 O12 (LLZO) and the incorporation of tellurium can accelerate the synthesis process by lowering the formation temperature of cubic LLZO at temperatures below 700 °C. Optimized synthesis at 750 °C showed a decrease in particle size and cell parameter for samples with higher amounts of Te and the evaluation of electrochemical performances reported for LLZO Te0.25 a value of ionic conductivity of 5,15×10-5 â S cm-1 after hot-pressing at 700 °C, two orders of magnitude higher than commercial Al-LLZO undergoing the same working conditions, and the highest value at this densification temperature. Partial segregation of Te-rich phases occurs for high-temperature densification. Our study shows the advantages of Te insertion on the sintering process of LLZO garnet and demonstrates the achievement of highly conductive LLZO with a low-temperature treatment.
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We report the influence of the partial substitution of Ge with Ti on the properties of NASICON Li1.5Al0.5Ge1.5(PO4)3 (LAGP) nanofibers prepared by electrospinning. Replacing a small amount of Ge (up to 20%) with Ti is advantageous for enhancing both the purity and morphology of LAGP fibers, as observed by X-ray diffraction, electron microscopy and nuclear magnetic resonance spectroscopy. When Ti-substituted LAGP (LAGTP) fibers are used as filler to develop composite polymer electrolytes, the ionic conductivity at 20 °C improves by a factor of 1.5 compared to the plain polymer electrolyte. Additionally, above 40 °C the LAGTP fiber-based composite electrolytes were more conductive than the equivalent LAGP fiber-based one. We believe that these findings can make a substantial contribution to optimizing current methods and developing novel synthesis approaches for NASICON based electrolytes.
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We present the thermal evolution of two NASICON-type ceramics namely LATP (Li1+xAlxTi2-x(PO4)3) and LAGP (Li1+xAlxGe2-x(PO4)3) by monitoring the electrode-electrolyte interfaces (i.e., Li/LATP and Li/LAGP) at temperatures up to 330 °C via in situ scanning electron microscopy, post-mortem energy-dispersive spectroscopy, and X-ray diffraction. Upon melting of Li and contacting electrolytes, LAGP decomposes completely to form Li based alloys, while LATP is partially decomposed without alloying.
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Lithium batteries are electrochemical devices that are widely used as power sources. This history of their development focuses on the original development of lithium-ion batteries. In particular, we highlight the contributions of Professor Michel Armand related to the electrodes and electrolytes for lithium-ion batteries.
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Li-10 wt % Mg alloy (Li-10 Mg) is used as an anode material for a solid-state battery with excellent electrochemical performance and no evidence of dendrite formation during cycling. Thermal treatment of Li metal during manufacturing improves the interfacial contact between a Li metal electrode and solid electrolyte to achieve an all solid-state battery with increased performance. To understand the properties of the alloy passivation layer, this paper presents the first direct observation of its evolution at elevated temperatures (up to 325°C) by in situ scanning electron microscopy. We found that the morphology of the surface passivation layer was unchanged above the alloy melting point, while the bulk of the material below the surface was melted at the expected melting point, as confirmed by in situ electron backscatter diffraction. In situ heat treatment of Li-based materials could be a key method to improve battery performance.
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Dendrite formation, which could cause a battery short circuit, occurs in batteries that contain lithium metal anodes. In order to suppress dendrite growth, the use of electrolytes with a high shear modulus is suggested as an ionic conductive separator in batteries. One promising candidate for this application is Li7La3Zr2O12 (LLZO) because it has excellent mechanical properties and chemical stability. In this work, in situ scanning electron microscopy (SEM) technique was employed to monitor the interface behavior between lithium metal and LLZO electrolyte during cycling with pressure. Using the obtained SEM images, videos were created that show the inhomogeneous dissolution and deposition of lithium, which induce dendrite growth. The energy dispersive spectroscopy analyses of dendrites indicate the presence of Li, C, and O elements. Moreover, the cross-section mapping comparison of the LLZO shows the inhomogeneous distribution of La, Zr, and C after cycling that was caused by lithium loss near the Li electrode and possible side reactions. This work demonstrates the morphological and chemical evolution that occurs during cycling in a symmetrical Li-Li cell that contains LLZO. Although the superior mechanical properties of LLZO make it an excellent electrolyte candidate for batteries, the further improvement of the electrochemical stabilization of the garnet-lithium metal interface is suggested.
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Rechargeable batteries are essential elements for many applications, ranging from portable use up to electric vehicles. Among them, lithium-ion batteries have taken an increasing importance in the day life. However, they suffer of several limitations: safety concerns and risks of thermal runaway, cost, and high carbon footprint, starting with the extraction of the transition metals in ores with low metal content. These limitations were the motivation for an intensive research to replace the inorganic electrodes by organic electrodes. Subsequently, the disadvantages that are mentioned above are overcome, but are replaced by new ones, including the solubility of the organic molecules in the electrolytes and lower operational voltage. However, recent progress has been made. The lower voltage, even though it is partly compensated by a larger capacity density, may preclude the use of organic electrodes for electric vehicles, but the very long cycling lives and the fast kinetics reached recently suggest their use in grid storage and regulation, and possibly in hybrid electric vehicles (HEVs). The purpose of this work is to review the different results and strategies that are currently being used to obtain organic electrodes that make them competitive with lithium-ion batteries for such applications.
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A nanolayer of reactive propyl acrylate silane groups was deposited on a lithium surface by using a simple dipping method. The polymerization of cross-linkable silane groups with a layer of ally-ether-ramified polyethylene oxide was induced by UV light. SEM analysis revealed a good dispersion of silane groups grafted on the lithium surface and a layer of polymer of about 4â µm was obtained after casting and reticulation. The electrochemical performance for the unmodified and modified lithium electrodes were compared in symmetrical Li/LLZO/Li cells. Stable plating/stripping and low interfacial resistance were obtained when the modified lithium was utilized, indicating that the combination of silane and polymer deposition is promising to increase Li-metal/garnet contact.
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Integration of solar-energy harvesting and storage functions has attracted significant research attention, as it holds promise for ultimate development of light-chargeable devices. In this context, a functional nanocomposite anode that not only permits electrochemical energy storage through Li-ion photo-intercalation, but also exhibits potential for photoelectrochromic applications, was investigated. The nanocomposite is made of the Li-ion intercalation compound WO3 , thinly coated with TiO2 and sensitized by the photoactive semiconductor CdS. During light exposure, the photoelectrons from CdS are transported to the WO3 /electrolyte interface, where Li-ion intercalation takes place. Photoelectron transport is facilitated by the interfacial TiO2 layer. The WO3 was shown to be functional in multiple photocharge-discharge cycles, but the CdS suffers from degradation and photocorrosion. Hence, the selection of compatible semiconductors and protective coating strategies should be pursued to overcome these issues.
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Most of the current commercialized lithium batteries employ liquid electrolytes, despite their vulnerability to battery fire hazards, because they avoid the formation of dendrites on the anode side, which is commonly encountered in solid-state batteries. In a review two years ago, we focused on the challenges and issues facing lithium metal for solid-state rechargeable batteries, pointed to the progress made in addressing this drawback, and concluded that a situation could be envisioned where solid-state batteries would again win over liquid batteries for different applications in the near future. However, an additional drawback of solid-state batteries is the lower ionic conductivity of the electrolyte. Therefore, extensive research efforts have been invested in the last few years to overcome this problem, the reward of which has been significant progress. It is the purpose of this review to report these recent works and the state of the art on solid electrolytes. In addition to solid electrolytes stricto sensu, there are other electrolytes that are mainly solids, but with some added liquid. In some cases, the amount of liquid added is only on the microliter scale; the addition of liquid is aimed at only improving the contact between a solid-state electrolyte and an electrode, for instance. In some other cases, the amount of liquid is larger, as in the case of gel polymers. It is also an acceptable solution if the amount of liquid is small enough to maintain the safety of the cell; such cases are also considered in this review. Different chemistries are examined, including not only Li-air, Li-O2, and Li-S, but also sodium-ion batteries, which are also subject to intensive research. The challenges toward commercialization are also considered.
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Organic cathode materials for lithium batteries are becoming increasingly popular because they have high theoretical redox voltage, high gravimetric capacity, low cost, easy processing and sustainability. However, their development is limited by their solubility in the electrolyte, which leads to rapid deterioration of the battery upon cycling. We developed a Janus membrane, which consists of two layers - a commercial polypropylene separator (Celgard) and a 300-600 nm layer of exfoliated graphite that was applied by a simple and environmentally friendly process. The submicron graphite layer is only permeable to Li+ and it drastically improves the battery performance, as measured by capacity retention and high coulombic efficiency, even at 2C rates. Post-mortem analysis of the battery indicates that the new membrane protects the anode against corrosion, and cathode dissolution is reduced. This graphite-based membrane is expected to greatly expedite the deployment of batteries with organic cathodes.