Recent advances in the electrolytes for interfacial stability of high-voltage cathodes in lithium-ion batteries
TL;DR: In this article, the authors describe several challenges for the cathode (spinel lithium manganese oxide (LMO), lithium cobalt oxide (LCO), lithium nickel cobalt manganes oxide (NCM), spinel lithium ion ion oxide (SILO), and lithium-rich layered oxide (Li-rich cathode))-electrolyte interfaces and highlight the recent progress in the use of oxidative additives and highvoltage solvents in high-performance cells.
Abstract: Advanced electrolytes with unique functions such as in situ formation of a stable artificial solid electrolyte interphase (SEI) layer on the anode and the cathode, and the improvement in oxidation stability of the electrolyte have recently gained recognition as a promising means for highly reliable lithium-ion batteries with high energy density. In this review, we describe several challenges for the cathode (spinel lithium manganese oxide (LMO), lithium cobalt oxide (LCO), lithium nickel cobalt manganese oxide (NCM), spinel lithium manganese nickel oxide (LNMO), and lithium-rich layered oxide (Li-rich cathode))-electrolyte interfaces and highlight the recent progress in the use of oxidative additives and high-voltage solvents in high-performance cells.
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TL;DR: This review gives an account of the various emerging high-voltage positive electrode materials that have the potential to satisfy the requirements of lithium-ion batteries either in the short or long term, including nickel-rich layered oxides, lithium- rich layeredOxides, high- voltage spinel oxide compounds, and high- voltage polyanionic compounds.
Abstract: The ever-growing demand for advanced rechargeable lithium-ion batteries in portable electronics and electric vehicles has spurred intensive research efforts over the past decade. The key to sustaining the progress in Li-ion batteries lies in the quest for safe, low-cost positive electrode (cathode) materials with desirable energy and power capabilities. One approach to boost the energy and power densities of batteries is to increase the output voltage while maintaining a high capacity, fast charge–discharge rate, and long service life. This review gives an account of the various emerging high-voltage positive electrode materials that have the potential to satisfy these requirements either in the short or long term, including nickel-rich layered oxides, lithium-rich layered oxides, high-voltage spinel oxides, and high-voltage polyanionic compounds. The key barriers and the corresponding strategies for the practical viability of these cathode materials are discussed along with the optimization of electrolytes and other cell components, with a particular emphasis on recent advances in the literature. A concise perspective with respect to plausible strategies for future developments in the field is also provided.
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TL;DR: This Review gives an overview of the various functional additives that are being applied in lithium metal rechargeable batteries and aims to stimulate new avenues for the practical realization of these appealing devices.
Abstract: Lithium metal (Li0 ) rechargeable batteries (LMBs), such as systems with a Li0 anode and intercalation and/or conversion type cathode, lithium-sulfur (Li-S), and lithium-oxygen (O2 )/air (Li-O2 /air) batteries, are becoming increasingly important for electrifying the modern transportation system, with the aim of sustainable mobility. Although some rechargeable LMBs (e.g. Li0 /LiFePO4 batteries from Bollore Bluecar, Li-S batteries from OXIS Energy and Sion Power) are already commercially viable in niche applications, their large-scale deployment is hampered by a number of formidable challenges, including growth of lithium dendrites, electrolyte instability towards high voltage intercalation-type cathodes, the poor electronic and ionic conductivities of sulfur (S8 ) and O2 , as well as their corresponding reduction products (e.g. Li2 S and Li2 O), dissolution, and shuttling of polysulfide (PS) intermediates. This leads to a short lifecycle, low coulombic/energy efficiency, poor safety, and a high self-discharge rate. The use of electrolyte additives is considered one of the most economical and effective approaches for circumventing these problems. This Review gives an overview of the various functional additives that are being applied and aims to stimulate new avenues for the practical realization of these appealing devices.
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TL;DR: In this paper, the authors evaluated the performance of a lithium metal anode in a vinylene carbonate (VC)-containing electrolyte using Li/Ni and LiCoO 2 /Li coin type cells.
350 citations
TL;DR: The results imply the functional mechanism of surface coatings, for example, AlF3, which can protect the electrode from etching by acidic species in the electrolyte, suppress cathode corrosion/fragmentation, and thus improve long-term cycling stability.
Abstract: The Li-rich, Mn-rich (LMR) layered structure materials exhibit very high discharge capacities exceeding 250 mAh g–1 and are very promising cathodes to be used in lithium ion batteries. However, significant barriers, such as voltage fade and low rate capability, still need to be overcome before the practical applications of these materials. A detailed study of the voltage/capacity fading mechanism will be beneficial for further tailoring the electrode structure and thus improving the electrochemical performances of these layered cathodes. Here, we report detailed studies of structural changes of LMR layered cathode Li[Li0.2Ni0.2Mn0.6]O2 after long-term cycling by aberration-corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). The fundamental findings provide new insights into capacity/voltage fading mechanism of Li[Li0.2Ni0.2Mn0.6]O2. Sponge-like structure and fragmented pieces were found on the surface of cathode after extended cycling. Formation of Mn2+...
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TL;DR: In this article, the decomposition of LiPF6 electrolytes with water was studied by measuring the water content after storage, and the experimental results were in good agreement with −d[H2O]/dt −=k[H 2O]2[LiPF6].
325 citations
TL;DR: In this article, a survey of the chemical stability of high surface area LiMn{sub 2}O{sub 4} in various Li-based electrolytes was performed as a function of temperature.
Abstract: A survey of the chemical stability of high-surface area LiMn{sub 2}O{sub 4} in various Li-based electrolytes was performed as a function of temperature. The evidence for an acidic-induced Mn dissolution was confirmed, but more importantly the authors identified, by means of combined infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction measurements, the growth, upon storage of LiMn{sub 2}O{sub 4} in the electrolyte at 100 C, of a protonated {lambda}-MnO{sub 2} phase partially inactive with respect to lithium intercalation. This results sheds light on how the mechanism of high temperature irreversible capacity loss proceeds. Mn dissolution first occurs, leading to a deficient spinel having all the Mn in the +4 oxidation state. Once this composition is reached, Mn cannot be oxidized further, and a protonic ion-exchange reaction takes place at the expense of the delithiation reaction. The resulting protonated {lambda}-Mn{sub 2{minus}y}O{sub 4} phase has a reduced capacity with respect to lithium, thereby accounting for some of the irreversible capacity loss experienced at 55 C for such a material.
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TL;DR: In this article, the effect of vinylene carbonate (VC) as electrolyte additive on the formation mechanisms of passivation films covering both electrodes in lithium-ion batteries was investigated by X-ray photoelectron spectroscopy (XPS).
Abstract: The effect of vinylene carbonate (VC) as electrolyte additive on the formation mechanisms of passivation films covering both electrodes in lithium-ion batteries was investigated by X-ray photoelectron spectroscopy (XPS). LiCo O2 /graphite coin cells using a LiP F6 /ethylene carbonate:diethyl carbonate:dimethyl carbonate liquid electrolyte with or without VC were charged at 20 and 60°C. The identification of VC-derived products formed at the surface of the electrodes was carried out by a dual experimental/theoretical approach. From a classical XPS core peak analysis completed by a detailed interpretation and simulation of valence spectra supported by ab initio calculations, and through direct synthesis of the VC polymer, we could evidence the formation of the radical poly(VC) at the electrode/electrolyte interfaces. We showed that the radical polymerization is the main reaction mechanism of VC contributing to the formation of the passivation layers at the surface of both electrodes. © 2008 The Electrochemical Society.
303 citations