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 article, 1,3,5-trihydroxybenzene (THB) is examined as a film-forming additive for over-lithiated layered oxide positive electrode.
37 citations
TL;DR: In this paper, surface characterization using ex situ X-ray photoelectron spectroscopy reveals that surface Mn 4+ -abundance induces the formation of new surface components and the passivation of cathode surface before being reduced to Mn 3+ to Mn 2+, leading to capacity retention 90% with discharge capacities 102-90 mAh/g over 50 cycles.
Abstract: The Mn 4+ -abundant surface of the Li- and Al-substituted spinel cathode materials is found to provide electrochemical and interfacial stabilities in the voltage region of 3.3-4.3 V vs. Li/Li + in the room temperature electrolyte of 1M LiPF 6 /EC:DEC. Surface characterization using ex situ X-ray photoelectron spectroscopy reveals that surface Mn 4+ -abundance induces the formation of a plenty of new surface components and the passivation of cathode surface before being reduced to Mn 3+ to Mn 2+ , leading to capacity retention 90% with discharge capacities 102-90 mAh/g over 50 cycles. FTIR spectroscopic analysis results and scanning electron microscopic imaging ensure that the Mn 4+ -abundant surface is better passivated by solid electrolyte interphase (SEI) layer that is composed of mixed organic and inorganic compounds, resulting in somewhat preserved particle morphology. On the contrary, the cathodes with equal amounted surface Mn 4+ /Mn 3+ and Mn 3+ -abundant surface are readily subjected to severe interfacial reaction and particle morphology change accompanied by inferior surface coverage by surface species, which are responsible for a rapid capacity fade. The data contribute to a basic understanding of importance of surface control and its impact on the cycling performance of spinel-based cathode materials for lithium-ion batteries.
34 citations
TL;DR: In this article, LiMn2O4/C-based Li-ion cells suffer from a limited cycle-life and a poor storage performance at 55 °C, both in their charged and discharged states.
Abstract: LiMn2O4-based Li-ion cells suffer from a limited cycle-life and a poor storage performance at 55 °C, both in their charged and discharged states. To get some insight on the origin of the poor 55 °C storage performance, the voltage distribution through plastic Li-ion cells during electrochemical testing was monitored by means of 3-electrode type measurements. From these measurements, coupled with chemical analysis, X-ray diffraction and microscopy studies, one unambiguously concludes that the poor performance of LiMn2O4/C-cells at 55 °C in their discharged state is due to enhanced Mn dissolution that increases with increasing both the temperature and the electrolyte HF content. These results were confirmed by a chemical approach which consists in placing a fresh LiMn2O4 electrode into a 55 °C electrolyte solution. A mechanism, based on an ion-exchange reaction leading to the Mn dissolution is proposed to account for the poor storage performance of LiMn2O4/C Li-ion cells in their discharged state. In order to minimize the Mn dissolution, two surface treatments were performed. The first one consists in applying an inorganic borate glass composition to the LiMn2O4 surface, the second one in using an acetylacetone complexing agent.
30 citations
TL;DR: In this paper, methylene methanedisulfonate (MMDS) was used as an electrolyte additive to improve the thermal stability of LiMn 2 O 4 cathode.
24 citations
TL;DR: In this paper, 2-vinylpyridine was added to the electrolyte to suppress the degradation of graphite anode, which improved the battery performances. But, the performance of the battery was not as good as that of Li/Li+ batteries.
Abstract: For lithium-ion batteries of C/(spinel Li–Mn–O), the sever capacity loss occurs after storage of the battery at >50 °C. This is mainly due to degradation of the carbon which was induced by electroreduction of Mn(II) dissolved from the spinel; this step is followed by the irreversible electrochemical reaction at the graphite/(Mn deposits)/electrolyte interface. However, 2-vinylpyridine as an additive into the electrolyte was capable of suppressing this degradation of graphite anode, therefore, improved the battery performances. During the first charge, electropolymerization of 2-vinylpyridine from about 0.9 V vs Li/Li+ resulted in film formation of poly(2-vinylpyridine) on the anode surface. The polymer protected the graphite from dissolved Mn(II).
23 citations