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: XPS spectra reveal that EMS does not contribute to the surface film formation on the LiNi0.4Mn1.6O4 surface, which results in lower reversible capacity losses compared to sulfones, but are still important: 45% at 30 °C and 70-75% at 40 °C.
Abstract: 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 Mn2+ and Ni2+ 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 CO 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 Mn2+ and Ni2+ 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.
20 citations
TL;DR: In this article, LiBOB additive was investigated to improve the storage characteristics at elevated temperature and cycling performance of the cell with LiMn2O4 cathode, and an advanced electrolyte was developed.
18 citations
TL;DR: In this article, the phase transformation of both base LiMn 2 O 4 and LiCu x Mn 2-x O 4 -coated L 2 O O 4 composite during charging at 0.1, 0.5 and 1 C rate from 3 to 4.5 V was confirmed by the in situ synchrotron X-ray diffractometer.
Abstract: The precursor of LiMn 2 O 4 was calcined at 600°C for 10 h to form the semicrystallite LiMn 2 O 4 and mixed with Cu(CH 3 COO) 2 in deionized water. The mixture powders were then calcined at 870°C for 10 h to synthesize LiCu x Mn 2-x O 4 -coated LiMn 2 O 4 composite. The phase transformation of both base LiMn 2 O 4 and LiCu x Mn 2-x O 4 -coated LiMn 2 O 4 during charging at 0.1, 0.5, and 1 C rate from 3 to 4.5 V was confirmed by the in situ synchrotron X-ray diffractometer. The plateau potential difference between the base LiMn 2 O 4 and LiCu x Mn 2-x O 4 -coated LiMn 2 O 4 composite was 50 mV. The decrease of the plateau can be related to the fact that the kinetics of the LiCu x Mn 2-x O 4 -coated LiMn 2 O 4 composite cathode material was faster than that of the uncoated material. The cyclic voltammograms of two cells using the LiCu x Mn 2-x O 4 -coated LiMn 2 O 4 composite and the base composite as the working electrodes and lithium metal as the counter electrode was applied to measure the oxidation and reduction reaction of the 2016 coin cell during charge and discharge with a rate of 0.1 mV/s from 3 to 4.5 V. Both uncoated LiMn 2 O 4 and LiCu x Mn 2-x O 4 -coated LiMn 2 O 4 composite displayed two pairs of well-separated redox peaks, corresponding to two voltage plateaus.
13 citations
TL;DR: In this article, three types of spinel-based cathode powders, namely, LiMn2O4, Li1.07Mn1.93O4 and Li 1.06Al0.74O4 were examined with rotating ring-disc collection experiments to measure manganese dissolution and capacity losses in lithium-ion cells.
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