Ulderico Ulissi

Exceptional long-life performance of lithium-ion batteries using ionic liquid-based electrolytes

Advanced ionic liquid-based electrolytes are herein characterized for application in high performance lithium-ion batteries. The electrolytes based on either N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI), N-butyl-N-methylpyrrolidinium bis(fluoro-sulfonyl)imide (Pyr14FSI), N-methoxy-ethyl-N-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide (Pyr12O1TFSI) or N-N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEMETFSI) ionic liquids and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt are fully characterized in terms of ionic conductivity, viscosity, electrochemical properties and lithium-interphase stability. All IL-based electrolytes reveal suitable characteristics for application in batteries. Lithium half-cells, employing a LiFePO4 polyanionic cathode, show remarkable performance. In particular, relevant efficiency and rate-capability are observed for the Py14FSI–LiTFSI electrolyte, which is further characterized for application in a lithium-ion battery composed of the alloying Sn–C nanocomposite anode and LiFePO4 cathode. The IL-based full-cell delivers a maximum reversible capacity of about 160 mA h g−1 (versus cathode weight) at a working voltage of about 3 V, corresponding to an estimated practical energy of about 160 W h kg−1. The cell evidences outstanding electrochemical cycle life, i.e., extended over 2000 cycles without signs of decay, and satisfactory rate capability. This performance together with the high safety provided by the IL-electrolyte, olivine-structure cathode and Li-alloying anode, makes this cell chemistry well suited for application in new-generation electric and electronic devices.

A Long-Life Lithium Ion Battery with Enhanced Electrode/Electrolyte Interface by Using an Ionic Liquid Solution

In this paper, we report an advanced long-life lithium ion battery, employing a Pyr14 TFSI-LiTFSI non-flammable ionic liquid (IL) electrolyte, a nanostructured tin carbon (Sn-C) nanocomposite anode, and a layered LiNi1/3 Co1/3 Mn1/3 O2 (NMC) cathode. The IL-based electrolyte is characterized in terms of conductivity and viscosity at various temperatures, revealing a Vogel-Tammann-Fulcher (VTF) trend. Lithium half-cells employing the Sn-C anode and NMC cathode in the Pyr14 TFSI-LiTFSI electrolyte are investigated by galvanostatic cycling at various temperatures, demonstrating the full compatibility of the electrolyte with the selected electrode materials. The NMC and Sn-C electrodes are combined into a cathode-limited full cell, which is subjected to prolonged cycling at 40 °C, revealing a very stable capacity of about 140 mAh g(-1) and retention above 99 % over 400 cycles. The electrode/electrolyte interface is further characterized through a combination of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations upon cell cycling. The remarkable performances reported here definitively indicate that IL-based lithium ion cells are suitable batteries for application in electric vehicles.

Conversion/alloying lithium-ion anodes – Enhancing the energy density by transition metal doping

The development of alternative anodes is crucial for next generation lithium-ion batteries that can charge rapidly while maintaining high lithium storage capacity. Among the most promising candidates are conversion/alloying metal oxides like SnO2, for which, however, the irreversibility of the conversion reaction provides a great hurdle – not least with respect to the substantial charge loss and, thus, limited energy density. Herein, we report on the improved reversibility of the conversion reaction by incorporating a transition metal dopant like iron, cobalt, or manganese. While all these dopants provide substantially enhanced capacities due to their beneficial effect on the alloying and conversion reaction, a detailed comparison concerning the achievable capacity at lower voltages, i.e., less than 2.0 V, reveals that the careful selection of the dopant plays a decisive role for the achievable energy density on the full-cell level. In fact, the highest energy density is obtained when doping SnO2 with manganese rather than cobalt or iron because of its relatively lower redox potential and when setting the anodic cut-off to 1.5 V – despite the lower capacity. These results may serve as a general guideline when designing and evaluating alternatives for graphite – in particular, those including a conversion step.

Low‐Polarization Lithium–Oxygen Battery Using [DEME][TFSI] Ionic Liquid Electrolyte

The room-temperature molten salt mixture of N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl) imide ([DEME][TFSI]) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt is herein reported as electrolyte for application in Li-O2 batteries. The [DEME][TFSI]-LiTFSI solution is studied in terms of ionic conductivity, viscosity, electrochemical stability, and compatibility with lithium metal at 30 °C, 40 °C, and 60 °C. The electrolyte shows suitable properties for application in Li-O2 battery, allowing a reversible, low-polarization discharge-charge performance with a capacity of about 13 Ah g-1carbon in the positive electrode and coulombic efficiency approaching 100 %. The reversibility of the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) is demonstrated by ex situ XRD and SEM studies. Furthermore, the study of the cycling behavior of the Li-O2 cell using the [DEME][TFSI]-LiTFSI electrolyte at increasing temperatures (from 30 to 60 °C) evidences enhanced energy efficiency together with morphology changes of the deposited species at the working electrode. In addition, the use of carbon-coated Zn0.9 Fe0.1 O (TMO-C) lithium-conversion anode in an ionic-liquid-based Li-ion/oxygen configuration is preliminarily demonstrated.

Enabling Reversible (De-)lithiation of Aluminum via the Use of Bis(fluorosulfonyl)imide-based Electrolytes

Aluminum, a cost-effective and abundant metal capable of alloying with Li up to around 1000 mAh g-1 , is a very appealing anode material for high energy density lithium-ion batteries (LIBs). However, despite repeated efforts in the past three decades, reports presenting stable cycling performance are extremely rare. This study concerns recent findings on the highly reversible (de)lithiation of a micro-sized Al anode (m-Al) by using bis(fluorosulfonyl)imide (FSI)-based electrolytes. By using this kind of electrolyte, m-Al can deliver a specific capacity over 900 mAh g-1 and superior Coulombic efficiency (96.8 %) to traditional carbonate- and glyme-based electrolytes (87.8 % and 88.1 %, respectively), which represents the best performance ever obtained for an Al anode without sophisticated structure design. The significantly improved electrochemical performance, which paves the way to realizing high-performance Al-based high energy density LIBs, can be attributed the peculiar solid-electrolyte interphase (SEI) formed by the FSI-containing electrolyte.

New Electrode and Electrolyte Configurations for Lithium-Oxygen Battery

Cathode configurations reported herein are alternative to the most diffused ones for application in lithium-oxygen batteries, using an ionic liquid-based electrolyte. The electrodes employ high surface area conductive carbon as the reaction host, and polytetrafluoroethylene as the binding agent to enhance the oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) reversibility. Roll-pressed, self-standing electrodes (SSEs) and thinner, spray deposited electrodes (SDEs) are characterized in lithium-oxygen cells using an ionic liquid (IL) based electrolyte formed by mixing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bis(trifluoromethanesulfonyl)imide (DEMETFSI). The electrochemical results reveal reversible reactions for both electrode configurations, but improved electrochemical performance for the self-standing electrodes in lithium-oxygen cells. These electrodes show charge/discharge polarizations at 60 °C limited to 0.4 V, with capacity up to 1 mAh cm-2 and energy efficiency of about 88 %, while the spray deposited electrodes reveal, under the same conditions, a polarization of 0.6 V and energy efficiency of 80 %. The roll pressed electrode combined with the DEMETFSI-LiTFSI electrolyte and a composite Lix Sn-C alloy anode forms a full Li-ion oxygen cell showing extremely limited polarization, and remarkable energy efficiency.