Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for high-energy fluoride ion cells

Science ◽  
2018 ◽  
Vol 362 (6419) ◽  
pp. 1144-1148 ◽  
Author(s):  
Victoria K. Davis ◽  
Christopher M. Bates ◽  
Kaoru Omichi ◽  
Brett M. Savoie ◽  
Nebojša Momčilović ◽  
...  
Keyword(s):  
Room Temperature ◽  
Lithium Ion ◽  
High Energy ◽  
Liquid Electrolyte ◽  
Temperature Cycling ◽  
High Energy Density ◽  
Fluoride Ion ◽  
Metal Fluoride ◽  
Operating Voltage ◽  
Ion Conducting

Fluoride ion batteries are potential “next-generation” electrochemical storage devices that offer high energy density. At present, such batteries are limited to operation at high temperatures because suitable fluoride ion–conducting electrolytes are known only in the solid state. We report a liquid fluoride ion–conducting electrolyte with high ionic conductivity, wide operating voltage, and robust chemical stability based on dry tetraalkylammonium fluoride salts in ether solvents. Pairing this liquid electrolyte with a copper–lanthanum trifluoride (Cu@LaF3) core-shell cathode, we demonstrate reversible fluorination and defluorination reactions in a fluoride ion electrochemical cell cycled at room temperature. Fluoride ion–mediated electrochemistry offers a pathway toward developing capacities beyond that of lithium ion technology.

scholarly journals High Energy Density Rechargeable Aqueous Lithium Batteries with an Aqueous Hydroquinone Sulfonic Acid and Benzoquinone Sulfonic Acid Redox Couple Cathode

2021 ◽  
Vol 3 (1) ◽  
Author(s):  
Hiroki Takagi ◽  
Koichi Kakimoto ◽  
Daisuke Mori ◽  
Sou Taminato ◽  
Yasuo Takeda ◽  
...  
Keyword(s):  
Energy Density ◽  
Sulfonic Acid ◽  
Acetic Acid Solution ◽  
Lithium Ion ◽  
High Energy ◽  
Open Circuit ◽  
Redox Couple ◽  
High Energy Density ◽  
Aqueous Acetic Acid ◽  
Ion Conducting

The demand for high energy density rechargeable batteries beyond lithium-ion batteries has increased for electric vehicles. In the present study, a novel high energy density rechargeable aqueous lithium battery was proposed. The battery was composed of a lithium metal anode, a lithium-stable non-aqueous electrolyte, a water-stable lithium-ion conducting solid electrolyte of Li1.4Al0.4Ge0.2Ti1.4(PO4)3-epoxy-TiO2 separator, and a hydroquinone sulfonic acid (HQS)/benzoquinone sulfonic acid (BQS) redox couple in an aqueous acetic acid solution (HAc). An open-circuit voltage of 3.7 V at 25 °C was recorded, and the theoretical energy density of the battery based on the reaction 2Li + BQS + 2H2O = 2 LiOH + HQS was 833 Whkg-1, about two times higher than that of the lithium-ion battery. The battery was successfully cycled at 0.5 mA cm-2 and 25 °C with low polarization.

scholarly journals Improving Cycle Life Through Fast Formation Using a Super-Concentrated Phosphonium Based Ionic Liquid Electrolyte for Anode-Free and Lithium Metal Batteries

2021 ◽  
Author(s):  
Thushan Pathirana ◽  
Dmitrii Rakov ◽  
Fangfang Chen ◽  
Maria Forsyth ◽  
Robert Kerr ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Energy Density ◽  
Electrochemical Impedance ◽  
Cell Formation ◽  
Lithium Ion ◽  
High Energy ◽  
Liquid Electrolyte ◽  
High Energy Density ◽  
Lithium Metal ◽  
Ionic Liquid Electrolyte

<p>ABSTRACT </p><p>Cell formation of lithium-ion cells impacts the evolution of the solid electrolyte interphase (SEI) and the cell cycle stability. Lithium metal anodes are an important step in the development of high energy density batteries owing to the high theoretical specific capacity of lithium metal. However, most lithium metal battery research has used a conventional lithium-ion formation protocol; this is time consuming, costly and does not account for the different properties of the lithium metal electrode. Here, we have used a recently reported promising phosphonium bis(fluorosulfonyl)imide ionic liquid electrolyte coupled with an NMC622 high areal capacity cathode (>3.5 mAh/cm2) to investigate the effect of cell formation rates. A faster formation protocol comprised of a pulsed 1.25C current decreased the formation time by 56 % and gave a 38 % greater capacity retention after 50 cycles when compared to formation at C/20. Electrochemical impedance spectroscopy measurements showed that the fast formation gave rise to a lower-resistance SEI. Column-like lithium deposits with reduced porous lithium domains between the particles were observed using scanning electron microscope imaging. To underline the excellent performance of these high energy-density cells, a 56 % greater stack specific energy was achieved compared to the analogous graphite-based lithium-ion cell chemistries. </p>

Enhanced Performance Induced by Phase Transition of Li2FeSiO4 upon Cycling at High Temperature

2020 ◽  
Author(s):  
Titus Masese ◽  
Yuki Orikasa ◽  
Kentaro Yamamoto ◽  
Yosuke Horie ◽  
Rika Hagiwara ◽  
...  
Keyword(s):  
Phase Transition ◽  
Phase Transformation ◽  
High Temperature ◽  
High Temperatures ◽  
Room Temperature ◽  
High Energy ◽  
Temperature Cycling ◽  
High Energy Density ◽  
Slow Phase ◽  
Rate Performance

<p>Owing to its low cost, thermal stability and theoretically high capacity, Li<sub>2</sub>FeSiO<sub>4 </sub>has been a promising cathode material for high-energy-density Li-ion (Li<sup>+</sup>) battery system. However, its poor rate performance and high voltage polarisation attributed to innately slow Li<sup>+</sup> kinetics at room temperature, has fundamentally curbed its ascent into prominence. Here, the rate performance of Li<sub>2</sub>FeSiO<sub>4</sub> at high temperatures in electrolyte comprising molten salt (ionic liquid) was investigated. Subsequently, a comparison of the phase transition behaviour observed at both high-temperature and room-temperature cycling was elucidated. Our results show that remarkable rate performance with good cyclability in conjunction with low voltage polarisation is attained upon cycling of Li<sub>2</sub>FeSiO<sub>4</sub> at high temperatures, due to the faster phase transformation from unstable monoclinic structures to thermodynamically stable orthorhombic structures triggered by elevated temperature. What this study adds to the burgeoning body of research work relating to the silicates is that the initially slow phase transformation behaviour observed at room temperature can significantly be enhanced upon cycling at elevated temperatures.</p>

scholarly journals Ordered LiNi0.5Mn1.5O4 Cathode in Bis(fluorosulfonyl)imide-Based Ionic Liquid Electrolyte: Importance of the Cathode-Electrolyte Interphase

2020 ◽  
Author(s):  
Hyeon Jeong Lee ◽  
Zachary Brown ◽  
Ying Zhao ◽  
Jack Fawdon ◽  
Weixin Song ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
High Voltage ◽  
Rate Capability ◽  
Lithium Ion ◽  
Cycling Performance ◽  
High Energy ◽  
Liquid Electrolyte ◽  
High Energy Density ◽  
X Ray ◽  
Ionic Liquid Electrolyte

<div><div><div><p>The high voltage (4.7 V vs. Li+ /Li) spinel lithium nickel manganese oxide (LiNi0.5 Mn1.5 O4 , LNMO) is a promising candidate for the next-generation of lithium ion batteries due to its high energy density, low cost and environmental impact. However, poor cycling performance at high cutoff potentials limits its commercialization. Herein, hollow structured LNMO is synergistically paired with an ionic liquid electrolyte, 1M lithium bis(fluorosulfonyl)imide (LiFSI) in N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (Pyr1,3 FSI) to achieve stable cycling performance and improved rate capability. The optimized cathode-electrolyte system exhibits extended cycling performance (>85% capacity retention after 300 cycles) and high rate performance (106.2mAhg–1 at 5C) even at an elevated temperature of 65 ◦C. X-ray photoelectron spectroscopy and spatially resolved x-ray fluorescence analyses confirm the formation of a robust, LiF-rich cathode electrolyte interphase. This study presents a comprehensive design strategy to improve the electrochemical performance of high-voltage cathode materials.</p></div></div></div>

scholarly journals DEVELOPMENT AND RESEARCH OF COMPOSITE ELECTROLYTE BASED ON LATP/LIPF6 SYSTEM FOR LITHIUM BATTERIES

2020 ◽  
Vol 86 (10) ◽  
pp. 75-87
Author(s):  
Ivan Lisovskyi ◽  
Serhii Solopan ◽  
Anatolii Belous ◽  
Volodymyr Khomenko ◽  
Viacheslav Barsukov
Keyword(s):  
Cathode Material ◽  
Lithium Ion Batteries ◽  
Lithium Ion ◽  
High Energy ◽  
Liquid Electrolyte ◽  
High Energy Density ◽  
Composite Electrolyte ◽  
Power Sources ◽  
Ceramic Electrolyte ◽  
Two Samples

Electrochemical power sources (EPSs) have been an integral part of every modern person’s life for a long time. Lithium-ion batteries (LIB) are the most common among the modern EPSs. They are widely used in the various electronic devices such as smartphones, cameras, laptops, electric vehicles etc. LIBs are considered to be the best power sources for mass use due to their high energy density. However, the low level of safety has always been a weakness of the conventional lithium-ion batteries with a polymer separator impregnated with a liquid electrolyte. The paper shows the fundamental possibility to develop the lithium-ion batteries with a composite electrolyte based on a porous ceramic matrix LATP, impregnated with 1M solution of LiPF6 in a mixture of ethylene carbonate and dimethyl carbonate (1:1). Two samples of composite electrolyte of different thickness (0.8 mm and 1.6 mm) were produced. The specific capacity of the cathode material in the elements with a composite electrolyte equals 140.5 and 138.2 mAh/g, which is not significantly less than the corresponding value for the cells with a liquid electrolyte (145.6 mAh/g). The decrease in the capacity of the cathode material in the elements with a composite electrolyte is primarily connected with the non-optimal thickness of the ceramic electrolyte and, accordingly, with the increase in the internal resistance of the cell. It is established that prototypes of lithium-ion batteries with a composite electrolyte show higher stability of capacitive characteristics during long cycling. Also, the proposed composite electrolyte allows solving the problems of lithium-ion batteries associated with electrolyte leakage (liquid electrolyte is immobilized only in the pores of ceramics) and fire hazard, primarily by levelling the formation of lithium dendrites in the interelectrode space. Further research will be aimed at the reducing the thickness of the ceramic electrolyte and developing a process for applying a protective layer to eliminate the recovery of LATP with lithium metal.

scholarly journals Origins of Large Voltage Hysteresis in High-Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes

2016 ◽  
Vol 138 (8) ◽  
pp. 2838-2848 ◽  
Author(s):  
Linsen Li ◽  
Ryan Jacobs ◽  
Peng Gao ◽  
Liyang Gan ◽  
Feng Wang ◽  
...  
Keyword(s):  
Energy Density ◽  
Lithium Ion Battery ◽  
Lithium Ion ◽  
High Energy ◽  
High Energy Density ◽  
Metal Fluoride ◽  
Voltage Hysteresis

Enhanced Performance Induced by Phase Transition of Li2FeSiO4 upon Cycling at High Temperature

2020 ◽  
Author(s):  
Titus Masese ◽  
Yuki Orikasa ◽  
Kentaro Yamamoto ◽  
Yosuke Horie ◽  
Rika Hagiwara ◽  
...  
Keyword(s):  
Phase Transition ◽  
Phase Transformation ◽  
High Temperature ◽  
High Temperatures ◽  
Room Temperature ◽  
High Energy ◽  
Temperature Cycling ◽  
High Energy Density ◽  
Slow Phase ◽  
Rate Performance

<p>Owing to its low cost, thermal stability and theoretically high capacity, Li<sub>2</sub>FeSiO<sub>4 </sub>has been a promising cathode material for high-energy-density Li-ion (Li<sup>+</sup>) battery system. However, its poor rate performance and high voltage polarisation attributed to innately slow Li<sup>+</sup> kinetics at room temperature, has fundamentally curbed its ascent into prominence. Here, the rate performance of Li<sub>2</sub>FeSiO<sub>4</sub> at high temperatures in electrolyte comprising molten salt (ionic liquid) was investigated. Subsequently, a comparison of the phase transition behaviour observed at both high-temperature and room-temperature cycling was elucidated. Our results show that remarkable rate performance with good cyclability in conjunction with low voltage polarisation is attained upon cycling of Li<sub>2</sub>FeSiO<sub>4</sub> at high temperatures, due to the faster phase transformation from unstable monoclinic structures to thermodynamically stable orthorhombic structures triggered by elevated temperature. What this study adds to the burgeoning body of research work relating to the silicates is that the initially slow phase transformation behaviour observed at room temperature can significantly be enhanced upon cycling at elevated temperatures.</p>

scholarly journals Improving Cycle Life Through Fast Formation Using a Super-Concentrated Phosphonium Based Ionic Liquid Electrolyte for Anode-Free and Lithium Metal Batteries

2021 ◽  
Author(s):  
Thushan Pathirana ◽  
Dmitrii Rakov ◽  
Fangfang Chen ◽  
Maria Forsyth ◽  
Robert Kerr ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Energy Density ◽  
Electrochemical Impedance ◽  
Cell Formation ◽  
Lithium Ion ◽  
High Energy ◽  
Liquid Electrolyte ◽  
High Energy Density ◽  
Lithium Metal ◽  
Ionic Liquid Electrolyte

<p>ABSTRACT </p><p>Cell formation of lithium-ion cells impacts the evolution of the solid electrolyte interphase (SEI) and the cell cycle stability. Lithium metal anodes are an important step in the development of high energy density batteries owing to the high theoretical specific capacity of lithium metal. However, most lithium metal battery research has used a conventional lithium-ion formation protocol; this is time consuming, costly and does not account for the different properties of the lithium metal electrode. Here, we have used a recently reported promising phosphonium bis(fluorosulfonyl)imide ionic liquid electrolyte coupled with an NMC622 high areal capacity cathode (>3.5 mAh/cm2) to investigate the effect of cell formation rates. A faster formation protocol comprised of a pulsed 1.25C current decreased the formation time by 56 % and gave a 38 % greater capacity retention after 50 cycles when compared to formation at C/20. Electrochemical impedance spectroscopy measurements showed that the fast formation gave rise to a lower-resistance SEI. Column-like lithium deposits with reduced porous lithium domains between the particles were observed using scanning electron microscope imaging. To underline the excellent performance of these high energy-density cells, a 56 % greater stack specific energy was achieved compared to the analogous graphite-based lithium-ion cell chemistries. </p>

scholarly journals Ordered LiNi0.5Mn1.5O4 Cathode in Bis(fluorosulfonyl)imide-Based Ionic Liquid Electrolyte: Importance of the Cathode-Electrolyte Interphase

2020 ◽  
Author(s):  
Hyeon Jeong Lee ◽  
Zachary Brown ◽  
Ying Zhao ◽  
Jack Fawdon ◽  
Weixin Song ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
High Voltage ◽  
Rate Capability ◽  
Lithium Ion ◽  
Cycling Performance ◽  
High Energy ◽  
Liquid Electrolyte ◽  
High Energy Density ◽  
X Ray ◽  
Ionic Liquid Electrolyte

<div><div><div><p>The high voltage (4.7 V vs. Li+ /Li) spinel lithium nickel manganese oxide (LiNi0.5 Mn1.5 O4 , LNMO) is a promising candidate for the next-generation of lithium ion batteries due to its high energy density, low cost and environmental impact. However, poor cycling performance at high cutoff potentials limits its commercialization. Herein, hollow structured LNMO is synergistically paired with an ionic liquid electrolyte, 1M lithium bis(fluorosulfonyl)imide (LiFSI) in N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide (Pyr1,3 FSI) to achieve stable cycling performance and improved rate capability. The optimized cathode-electrolyte system exhibits extended cycling performance (>85% capacity retention after 300 cycles) and high rate performance (106.2mAhg–1 at 5C) even at an elevated temperature of 65 ◦C. X-ray photoelectron spectroscopy and spatially resolved x-ray fluorescence analyses confirm the formation of a robust, LiF-rich cathode electrolyte interphase. This study presents a comprehensive design strategy to improve the electrochemical performance of high-voltage cathode materials.</p></div></div></div>

Numerical Study of Composite Electrode's Particle Size Effect on the Electrochemical and Heat Generation of a Li-Ion Battery

2015 ◽  
Vol 6 (4) ◽  
Author(s):  
A. H. N. Shirazi ◽  
M. R. Azadi Kakavand ◽  
T. Rabczuk
Keyword(s):  
Heat Generation ◽  
Numerical Study ◽  
Lithium Ion ◽  
High Energy ◽  
Solid Particles ◽  
High Energy Density ◽  
Design Parameters ◽  
Operating Voltage ◽  
Battery Cell ◽  
Battery Capacity

Rechargeable lithium-ion batteries (LIBs) are now playing crucial roles in power supply and energy storage systems. Among all types of rechargeable batteries available nowadays, LIBs are one of the most important ways to store energy because of their high energy density, high operating voltage, and low rate of self-discharge. Nonetheless, the performance of LIBs could be improved by different design parameters, such as the size of solid particles in the battery composite electrodes. Therefore, this study aims to investigate the effect of the composite electrode particles size on the electrochemical and heat generation of an LIB. A Newman's electrochemical pseudo two-dimenisonal model was used to model the LIB cell. Reversible heat produced through electrochemical reactions was calculated as well as irreversible heat originating from internal resistances in the battery cell. Our results show that smaller sizes of electrode solid particles improve the thermal characteristics of the battery, especially in higher charge and discharge currents (C-rate). Furthermore, as the solid particle sizes decrease, the battery capacity increases for various C-rates in charge and discharge cycles.

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