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, the reaction of an electrolyte (1 M LiPF 6 in ethylene carbonate/dimethyl carbonates/diethyl carbonate, 1:1:1) with the surface of LiNi 0.5 Mn 1.5 O 4 at various voltages (4.0-5.3 V vs Li) was investigated.
Abstract: The reaction of an electrolyte (1 M LiPF 6 in ethylene carbonate/dimethyl carbonate/diethyl carbonate, 1:1:1) with the surface of LiNi 0.5 Mn 1.5 O 4 at various voltages (4.0-5.3 V vs Li) was investigated. Coin cells (Li/LiNi 0.5 Mn 1.5 O 4 ) stored at low voltage (4.0-4.5 V vs Li) show low residual current, and ex situ analysis of the LiNi 0.5 Mn 1.5 O 4 surface by X-ray photoelectron spectroscopy (XPS) and IR spectroscopy suggests low concentrations of electrolyte decomposition products. Coin cells (Li/LiNi 0.5 Mn 1.5 O 4 ) stored at high voltage (4.7-5.3 V vs Li) show increased residual current, and ex situ analysis of the cathode surface by XPS and IR supports the presence of poly(ethylenecarbonate).
443 citations
TL;DR: The solid electrolyte interface (SEI) formation on composite graphite and highly oriented pyrolytic graphite in a vinylene carbonate (VC)-containing electrolyte was analyzed using evolved gas analysis, Fourier transform infrared analysis, two-dimensional nuclear magnetic resonance, X-ray photoelectron spectroscopy, time of flight secondary ion mass spectrometry, and scanning electron microscopy.
Abstract: The solid electrolyte interface (SEI) formation on composite graphite and highly oriented pyrolytic graphite in a vinylene carbonate (VC)-containing electrolyte was analyzed using evolved gas analysis, Fourier transform infrared analysis, two-dimensional nuclear magnetic resonance, X-ray photoelectron spectroscopy, time of flight-secondary-ion mass spectrometry, and scanning electron microscopy We found that the SEI layers derived from VC-containing electrolytes consist of polymer species such as poly (vinylene carbonate) (poly(VC)), an oligomer of VC, a ring-opening polymer of VC, and polyacetylene Moreover, lithium vinylene dicarbonate, (CHOCO 2 Li) 2 , lithium divinylene dicarbonate, (CH=CHOCO 2 Li) 2 , lithium divinylene dialkoxide, (CH=CHOLi) 2 , and lithium carboxylate, RCOOLi, were formed on graphite as VC reduction products The presence of VC in the ethylene carbonate (EC)-based electrolyte caused a decrease in the reductive gases of the EC dimethyl carbonate solvent such as C 2 H 4 , CH 4 , and CO The VC-derived SEI layer was formed at a potential more positive than 10 V vs Li/Li + Effective SEI formation by reduction of VC progresses before that of EC The thermal decomposition temperature of the SEI layer derived from VC shifted to a higher temperature compared to that derived from the VC-free electrolytes We concluded that the thermal stability of the VC-derived SEI layer has a close relation to high-temperature storage characteristics at elevated temperatures
435 citations
TL;DR: In this paper, a review of surface phenomena using in situ and ex situ FTIR spectroscopy, atomic force microscopy (in situ AFM), electrochemical quartz crystal microbalance (EQCM), and impedance spectrography (EIS) is presented.
417 citations
TL;DR: In this paper, structural fatigue has been detected at the surface of discharged Li{sub x}[Mn{sub 2}]O{sub 4} spinel electrodes in (4 V) Li/Li{sub X][mn{ sub 2]O[sub 4] cells.
Abstract: Evidence of structural fatigue has been detected at the surface of discharged Li{sub x}[Mn{sub 2}]O{sub 4} spinel electrodes in (4 V) Li/Li{sub x}[Mn{sub 2}]O{sub 4} cells. Under nonequilibrium conditions, domains of tetragonal Li{sub 2}[Mn{sub 2}]O{sub 4} coexist with cubic Li[Mn{sub 2}]O{sub 4}, even at 500mV above the thermodynamic voltage expected for the onset of the tetragonal phase. The presence of Li{sub 2}[Mn{sub 2}]O{sub 4} on the particle surface may contribute to some of the capacity fade observed during cycling of Li/Li{sub x}[Mn{sub 2}]O{sub 4} cells.
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TL;DR: The direct observation of Li2O formation during the extended plateau is demonstrated and the consequences of its formation on the cathode and anode are discussed and protection from, or mitigation of, such devastating surface reactions on both electrodes will be necessary to help realize the potential of high-capacity cathode materials.
Abstract: High-capacity layered, lithium-rich oxide cathodes show great promise for use as positive electrode materials for rechargeable lithium ion batteries. Understanding the effects of oxygen activating reactions on the cathode’s surface during electrochemical cycling can lead to improvements in stability and performance. We used in situ surfaced-enhanced Raman spectroscopy (SERS) to observe the oxygen-related surface reactions that occur during electrochemical cycling on lithium-rich cathodes. Here, we demonstrate the direct observation of Li2O formation during the extended plateau and discuss the consequences of its formation on the cathode and anode. The formation of Li2O on the cathode leads to the formation of species related to the generation of H2O together with LiOH and to changes within the electrolyte, which eventually result in diminished performance. Protection from, or mitigation of, such devastating surface reactions on both electrodes will be necessary to help realize the potential of high-capaci...
385 citations