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Investigation of Lithium Superoxide-Based Batteries

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Investigation of Lithium Superoxide-Based Batteries Investigation of Lithium Superoxide-Based Batteries P.I.: K. Amine L. Curtiss Argonne National Laboratory DOE merit review June 1-4, 2020 Project ID# BAT-431 This presentation does not contain any proprietary, confidential, or otherwise restricted information. Overview Timeline Barriers ▪ Start: 2019 ▪ Barriers addressed ▪ Finish: 2023 – Cycle life ▪ 60 % – Capacity – Efficiency Budget Partners • Total project funding • Interactions/ collaborations – DOE share: $ 1280 K • M. Asadi, IIT – Contractor 0 • S. Al-Hallaj and B. Chaplin, UIC • FY 18: $ 400 K • J. G. Wen, ANL • FY 19: $ 450 K • K. C. Lau University of • FY 20: $ 430 K California-Northridge • M. Asadi, IIT 2 Project Objectives and Relevance ▪ Investigation of Li-O2 batteries based on lithium superoxide to achieve understanding of discharge chemistry and how to enhance cycle life. ▪ Use an integrated approach based on experimental synthesis and state-of-the-art characterization combined with high level computational studies focused on materials design and understanding ▪ Li-air batteries based on lithium superoxide have the potential for being the basis for closed systems without need for an external O2 source 3 Milestones Month/ Milestones Year Characterization of electronic properties of high temperature Jun/20 synthesized Ir3Li, (Completed) Voltage profiles and characterization of discharge product by titration Sep/20 and other techniques in an Ir3Li cell, (Completed) TEM studies of large LiO particles, investigation of stability and Dec/21 2 formation mechanism, (Completed) Investigate performance of Li-O battery using cathode based on bulk Mar/21 2 high temperature synthesized IrLi particles on rGO support, (Initiated) 4 Strategy: an integrated experiment/theory approach that combines testing, understanding and design to develop lithium superoxide based Li-O2 batteries Synthesize, test, and Evaluate solvents, salts, and characterize cathode additives architectures Develop Develop understanding of understanding of the the synergies between discharge and charge electrolyte components mechanisms and cathode Design of improved cathodes/electrolytes for efficiency, cycle life, and capacity Experimental methods Synthesis ▪ New catalyst materials ▪ Electrolytes Characterization ▪ In situ XRD measurement (Advanced Photon Source) ▪ TEM imaging ▪ FTIR, Raman ▪ SEM imaging ▪ Impedance measurements ▪ Titration Testing ▪ Swagelok cells 6 Highly accurate quantum chemical modeling ▪ Periodic, molecular, and cluster calculations using density functional calculations ▪ Static calculations ▪ Ab initio molecular dynamics simulations (AIMD) ▪ Understanding discharge products ▪ Li2O2 structure and electronic properties ▪ LiO2 structure and electronic properties ▪ Design of electrolytes ▪ Reaction energies and barriers for stability screening ▪ Electrolyte/surface interface simulations 7 Background ▪ Previous studies of lithium superoxide based Li-O2 batteries have been based on Ir nanoparticles on a reduced graphene oxide (rGO) cathode that partially form Ir3Li during cycling, which act as templates for growth of LiO2 instead of the more stable Li2O2 product – Ir nanoparticles and different sizes : Lu, Amine, Curtiss, et al Nature 529, 377 (2016). – Size selected Ir clusters (Irn, n = 2-8) Lu, Vajda, Amine, Curtiss et al J. Phys. Chem A 123, 10047 (2019). – In both cases Li is partially incorporated into Ir particles during discharge ▪ In this work we have synthesized (at high temperatures) and characterized bulk IrLi3 and IrLi alloys using a high temperature method to use in LiO2 batteries Go to ”Insert (View) | Header and Footer" to add your organization, sponsor, meeting name here; then, click "Apply to All" 8 Summary of Technical Accomplishments 1. Characterization of electronic properties of Ir3Li particles relevant to use as catalysts in Li-O2 cells – Bulk Ir3Li was found to have comparable conductivity to iridium metal – Possess metal-like magnetic properties, and have an affinity toward O2. 2. Micron sized Ir3Li particles are used to stabilize large LiO2 particles of over 200 nm for first time – Use of large Ir3Li particles in a Li-O2 cell promotes a nucleation and growth mechanism that results in large ultra-nanocrystalline LiO2 particles in the discharge product – The large LiO2 particles are more stable than previously grown small LiO2 particles in Li-O2 cells 3. IrLi alloy found to give good cycling performance in a Li-O2 cell with LiO2 as the discharge product – 100 cycles with confirmation of LiO2 as a product Characterization of Bulk Ir3Li Synthesized at High Temperatures (500 nm to 5 microns): Raman spectroscopy and stability a * Ir * * Ir3Li * 100 150 200 250 * * RelativeRelativeRelative IntensityIntensityIntensity 100 200 300 400 500 600 Raman Shift (cm-1) (a)b Raman shift of Ir starting material and synthesized Ir3Li. (b) Calculated phonon density of states of Ir3Li with Ir-Li coupled modes (red trace) and vibration -1 ~128 cm ~138 cm-1 ~433 cm-1 ~435 cm-1 (A ) modes(A ) dominated(A ) by Li (green trace). 1 2 (B1) 1 (c) RamanIr-Li coupled spectra ofLi Ir3Li powder during extended exposure to air. vibration modes • These results show that Raman spectroscopy can be used to Phonon Phonon DensityPhonon DensityPhonon Density ofofof StatesStatesStates (PDOS)(PDOS)(PDOS) differentiate Ir3Li from Ir. 0 100 200 300 400 500 600 • RamanPhonon Frequency measurements (cm-1) performed on the sample after 12 hr, 96 hr and 4 c weeks of Initial exposure Test found that the Raman spectra was similar in all cases 12 hr Air Exposure indicating 96 hrthat Air Exposure bulk Ir3Li is stable in air for extended periods. 4 Week Air Exposure Go to ”Insert (View) | Header and Footer" to add your organization, sponsor, meeting name here; then, click "Apply to All" 10 RelativeRelativeRelative IntensityIntensityIntensity 200 400 600 800 Raman Shift (cm-1) Characterization of Bulk Ir3Li (500 nm to 5 microns): Magnetic susceptibility, heat capacity, and EPR 2.5 60 ] -1 50 oe a b ) -1 2.0 -1 40 (a) Magnetic susceptibility of Ir3Li (black K -1 -2 0.015 1.5 30 K -1 trace) with fitted curve (red trace) 0.010 (J mol 20 p 0.005 emu mol(f.u.) C 1.0 /T (J mol p -4 (b) heat capacity of Ir3Li 10 C 0.000 10 0 25 50 [ 2 2 c T (K ) 0.5 0 (c) EPR spectrum of iridium powder in O 0 20 40 60 80 100 120 0 50 100 150 200 250 2 T (K) T (K) atmosphere at 200 K 1x104 c g = 2.0008 g = 1.9797 d 4 O2 1x10 (d) Ir Li and Ir EPR spectrum in O 1x104 3 2 0 atmosphere at 100 K and 200K, 0 Intensity 0 g = 2.0394 Intensity respectively. 4 g = 2.0238 Intensity -1x10 Ir + O2 g = 1.9746 Ir3Li + O2 -1x104 -1x104 -2x104 3000 3200 3400 3600 3800 3000 3200 3400 3600 3800 Field G Field G • The magnetic susceptibility measurement together with heat capacity indicate that the temperature dependent behavior of Ir3Li is metallic, which is support for the ORR/OER properties of Ir3Li. • The EPR results suggest that both Ir and Ir3Li attract oxygen. Go to ”Insert (View) | Header and Footer" to add your organization, sponsor, meeting name here; then, click "Apply to All" 11 Characterization of Bulk Ir3Li (500 nm to 5 microns): XPS and AFM a b Ir 4f5/2 Ir 4f7/2 Intensity 70 68 66 64 62 60 58 56 Binding Energy (eV) (c) XPS spectra of Ir3Li powders showing three components of a Ir 4f7/2 peak at binding energy - (BE) 59.95 eV [Ir3 blue trace], 60.89 eV [Ir(0) green trace], and 63.99 eV [unknown impurity], respectively. (d) 5 x 5 μm current image of conductive AFM scan indicating high conductivity in bright color throughout the sample. • This XPS analysis suggests a charge distribution of Li ~ +0.81e and Ir ~ -0.25e. The negative Ir charge provides a higher tendency to donate electrons. The ORR reaction may be more facile when occurring on Ir3Li compared to IR. 7 • From AFM measurements the Ir3Li conductivity was determined as 2.5·10 S/m, which is similar to that of Ir metal. These results demonstrate the highly conductive nature of Ir3Li needed for a cathode material. Go to ”Insert (View) | Header and Footer" to add your organization, sponsor, meeting name here; then, click "Apply to All" 12 Li-O2 cell performance with micron size Ir3Li particles 5 5 a ba 1 2 cb 1 2 3 4 3 4 4 5 4 5 Voltage Voltage 3 3 2 2 0 200 400 600 800 1000 0 200 400 600 800 1000 Capacity (mAh/g) Capacity (mAh/g) 5 (a) SEM image of Ir3Li powders post grinding with mortar and pestle. Scaled bar is 10Spot μm. 1 c * LiO2 (b) The first five cycles of a Li-O cell with rGO/GDL cathode, 1 M Li triflate in TEGDME Spot 2 electrolyte and 2 4 Spot 3 2 * current density 0.05 mA/cm , showing a two-plateau charge profile * (c) The first five cycles of a Li-O2 cell withVoltage Ir3Li-rGO/GDL cathode showing an initial high charge potential toward the end of the 1st charge cycle which3 tapered down and reached a charge potential below 3.5 V by the fourth cycle. Same electrolyte and current density as in (b) were applied.Relative Intensity 2 0 500 1000 1500 800 1000 1200 1400 1600 1800 Capacity (mAh/g) Raman Shift (cm-1) • Ir3Li particles used in the cathode of the Li-O2 cell ranged from 200 nm to 5 microns • Voltage profiles show low charge potentials similar to previous Li-O2 cells based on much smaller Ir nanoparticles that gave LiO2 discharge product Go to ”Insert (View) | Header and Footer" to add your organization, sponsor, meeting name here; then, click "Apply to All" 13 Characterization of the Ir3Li- based Li-O2 cell discharge product by Raman and titration a 5 b 5 a 1 2 b 1 2 3 4 3 4 4 5 4 5 Voltage Voltage 3 3 2 2 0 200 400 600 800 1000 0 200 400 600 800 1000 Capacity (mAh/g) Capacity (mAh/g) 5 Spot 1 c d * LiO (a) Deep discharge of Ir3Li-rGO cathode in a Li-O2 cell showing the discharge Spot potential 2 ~2.752 V for use in characterization Spot 3 4 * (b) Raman spectra of deep discharged Ir3Li-rGO cathode in a Li-O2 cell showing* strong LiO2 Voltage peaks at different areas.
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