Bulletin of the American Physical Society
APS March Meeting 2020
Volume 65, Number 1
Monday–Friday, March 2–6, 2020; Denver, Colorado
Session B21: Energy Storage - Electrolyte Physics |
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Sponsoring Units: GERA Chair: Ryan Wixom, Sandia National Laboratories Room: 302 |
Monday, March 2, 2020 11:15AM - 11:27AM |
B21.00001: High Ionic Conductivity Composite Solid-State Electrolytes Ernesto Marinero, Andres Villa, Juan Carlos Verduzco We report on the development of a solid-state electrolyte (SSE) with high ionic conductivity, having physical properties that allow their ready integration into current battery devices whose fabrication is amenable to large scale manufacturing. The prototype Composite SSE reported comprises a polymer-Li-salt matrix embedded with super-ionically conducting garnet nanoparticles. We employ polyethylene-oxide (PEO) + LiTFSI (salt) as a matrix incorporating Bi-doped lithium lanthanum zirconium oxide (LLZBO) ceramic nanoparticles (~350nm diameter). We study the role of Bi-aliovalent substitution in LiLaZrO on the microstructure and the ionic conductivity of the ceramic garnet material. We successfully reduce the synthesis temperature of LiLaZrO by Bi-additions utilizing sol-gel reactions. Additions of very small amounts (5% weight load) of the garnet nanoparticles to the polymer-salt matrix result in over two-orders of magnitude increments of the ionic conductivity of the polymer-salt matrix. This composite SSE is amenable to large-scale fabrication and integration into battery devices, furthermore given the small amount of ceramic particles needed, it is cost-competitive. |
Monday, March 2, 2020 11:27AM - 11:39AM |
B21.00002: Understanding ionic diffusivity in (meta)stable (un)doped solid state electrolyte from first principles: A case study of LISICON (Li4SiO4) Deepika Gill
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Monday, March 2, 2020 11:39AM - 11:51AM |
B21.00003: Design of the sodium ionic conductor for all-solid-state battery Kazuyuki Kawahara, Satoshi Heguri The high ionic conductivity of solid electrolyte plays a key role in the performance of all-solid-state batteries. Therefore, the crystal structure is very important in the design of solid ionic conductor. Recently, various solid electrolytes for all-solid-state lithium-ion batteries, especially lithium thiophosphate system, have been reported. These materials generally exhibit high ionic conductivity and can be obtained by easy preparation methods. Kandagal et al. theoretically predicted a new sodium-ion conductor having same crystal structure of lithium thiophosphates [1]. To date, however, it has been not experimentally demonstrated. In the present study, we synthesize a new sodium-ion conductor using a mechanochemical technique and subsequent optimized thermal treatments. The details of the crystal structural analysis and characterization of the AC impedance will be discussed. |
Monday, March 2, 2020 11:51AM - 12:03PM |
B21.00004: First-principles study on electrode-contact chemical stability and Na ion dynamics of Na3SbS4 solid electrolyte for all-solid-state Na ion batteries Randy Jalem, Yoshitaka Tateyama To enhance safety, the replacement of the combustible organic-/liquid-based electrolyte in sodium ion batteries with a ceramic-based solid electrolyte has been sought. In this talk, we present our results on thermodynamic and ion dynamics analyses of Na3SbS4 solid electrolyte using first-principles calculations. Based from the calculated chemical potential diagram when Na3SbS4 is in contact with possible layered cathode compounds Na[TM]O2 (where TM = {V, Cr, Mn, Fe, Co, Ni}), sulfur has the driving force to migrate across the electrolyte-cathode interface which may partly explain the experimentally observed formation of interface reaction layer in such all-solid state battery interfaces. From space-time correlation analysis of molecular dynamics trajectory, we determined a concerted migration behavior for Na ions which can explain for the material's superionic conductivity behavior (>10-3 S/cm). The effects of halide doping on the conductivity behavior of Na3SbS4 will also be discussed. |
Monday, March 2, 2020 12:03PM - 12:15PM |
B21.00005: Tracking structural dynamics in operando sodium ion batteries Oleg Gorobtsov, Hayley Hirsh, Daniel Weinstock, Ryan Bouck, Dina Sheyfer, Ziyi Wang, Minghao Zhang, Wonsuk Cha, Ross Harder, Shirley Meng, Andrej Singer Sodium ion batteries are promising candidates for storage of energy produced by solar and wind sources. Alternative energy sources are by nature intermittent, and require storage facilities to compensate. Lithium ion batteries, while ubiquitous, are too expensive to satisfy this need. Sodium ion batteries promise to be a cheaper alternative to produce in mass. However, they currently suffer from much faster degradation than Li-ion batteries and often degrade after just a few charge-discharge cycles. Defects in the nanoparticles in lithium ion batteries have been studied by coherent diffraction imaging at X-ray sources (CXDI). We have applied CXDI to sodium ion batteries in operando and obtained information about the evolution of planar and linear defects in the nanoparticles in Na-ion battery cathodes, offering insights in how to improve the performance of Na-ion batteries. |
Monday, March 2, 2020 12:15PM - 12:27PM |
B21.00006: Prediction and analysis of a sodium ion electrolyte: Li2Na2P2S6 Yan Li, Zachary D Hood, Natalie A Holzwarth Recent experimental results of Hood et al.1 show that Na4P2S6, which crystallizes in the based-centered monoclinic structure C2/m (#12), has significant Na ion conductivity (3 × 10-6 S/cm) at room temperature. Using density functional theory and density functional perturbation theory within the harmonic phonon approximation, we predict that the Na ion conductivity can be enhanced by alloying this electrolyte with Li to form Li2Na2P2S6 having the same C2/m structure with compacted a and b lattice constants. The calculation of Helmholz free energies suggests that the alloy material is stable for a range of temperatures at and above room temperature in terms of the energy difference F(Li2Na2P2S6 + 2Na) − (F(Na4P2S6 + 2Li) ≤ −0.35 eV. Molecular dynamics simulations indicate that Li2Na2P2S6 has larger Na ion conductivity than does Na4P2S6 and therefore is promising as a possible solid-state electrolyte for all-solid-state Na ion batteries. |
Monday, March 2, 2020 12:27PM - 12:39PM |
B21.00007: Mg ion conducting solid polymer electrolyte for advanced energy storage system Meeta Trivedi, Hamad Albehaijan, Thein Kyu Magnesium (Mg) batteries have the potential to replace the Li-ion technology because of superior safety and high abundance of Mg metal. However, the commercialization is hindered due to lack in development of electrolyte and cathode systems. A novel highly conductive, solvent-free, solid state polymer Mg ion electrolyte for advanced energy storage application is developed. Mg-ion conducting solid state polymer electrolytes (SPE) comprised of polyethylene glycol diacrylate (PEGDA) prepolymer, magnesium bis(trifluoromethanesulfonyl) imide (Mg(TFSI)2) salt, and succinonitrile (SCN) plasticizer were systematically examined. Optimization of composition for solid polymer electrolyte to achieve superionic conductivity was performed in the isotropic region guided by ternary phase diagram. Addition of plasticizer decreases Tgof the system, but it increases the ionic conductivity. By using various plasticizers and mixed Mg/Li salts in the development of SPE, the effect of plasticization and salt composition on the ionic conductivity, electrochemical stability window, thermal stability and mechanical properties will be demonstrated. |
Monday, March 2, 2020 12:39PM - 12:51PM |
B21.00008: AC conductivity studies of polyethylene oxide-garnet-type Li7La3Zr2O12 hybrid composite solid polymer electrolyte films Parisa Bashiri, T. Prasada Rao Rao, Vaman Naik, Gholam Abbas Nazri, Ratna Naik We have investigated both AC dielectric permittivity and ionic conductivity of hybrid composite solid polymer electrolyte (CSPE) films (~100 mm) comprised of sub-micron sized aluminum substituted cubic Li7La3Zr2O12 (LLZO) particles dispersed in polyethylene oxide-LiClO4 (PEO-LiClO4) matrix with [EO]:[Li] = 15:1. The complex AC permittivity and conductivity were determined using the measured electrical impedance spectra in the range of 1 Hz to 300 kHz and analyzed using generalized power-law that accounts for the effect of electrode polarization. The ionic and segmental relaxation times obtained from fitting the experimental data indicate a strong coupling between the ionic motion and segmental dynamics. Further, the observed temperature dependent conductivity follows the Vogel-Tammann-Fulcher (VTF) behavior implying a close correlation between ionic conductivity and segmental relaxation in these polymer electrolytes. The VTF model yields an activation energy of 0.32 eV for PEO-LiClO4 film, and 0.07 eV for PEO-LLZO-LiClO4 composite film, consistent with the observed enhancement in conductivity by two orders of magnitude at 30 oC upon the addition of LLZO particles. Details preparation of CSPE films and the analyses will be presented. |
Monday, March 2, 2020 12:51PM - 1:03PM |
B21.00009: A solid 3D Li-S battery design via stacking 2D conductive microporous coordination polymers and amorphous Li-S layers Guoping Gao In order to make a Li-S battery practical, not only high gravimetric energy capacity is important, high volumetric energy capacity will also be required. The currently explored Li-S cathode designs often deploy systems with liquid electrolyte infiltration, hence with relatively low volumetric capacity. In the current study, we theoretically test a compact solid 3D design (more like a Li-ion battery cathode than a conventional Li-S cathode) consisted of a sandwich structure alternating between the 2D Mn-HAB layer and amorphous Li-S layer. We study the theoretical limits for both its gravimetric and volumetric energy capacity, as well as its structural stability and Li diffusion within the cathode system. In order to study the Li diffusion within an amorphous system, we also develop a pull-atom molecular dynamics (PA-MD) to calculate the barrier heights of such disordered systems. We reveal the mechanism which determines the Li diffusion in the amorphous layer of the system. Overall, we find such 3D solid Li-S cathode can be practical, with sufficient large gravimetric and volumetric energy capacity, as well as the Li diffusion constant. It also solves many other common Li-S cathode problems, from Li polysulfide dissolution, to electrical insulating, and structure instabilities. |
Monday, March 2, 2020 1:03PM - 1:15PM |
B21.00010: First Principles Study of Electrolyte Interactions in Calcium Ion Batteries Joshua Young, Peter Kulick, Taylor Juran, Manuel Smeu Multivalent ion batteries, which use species such as Ca as the working ion, are gaining increasing attention. Compared to other multivalent ions, Ca exhibits a reduction potential close to that of Li, high volumetric capacity, and faster diffusion. However, the breakdown of organic electrolytes causes a passivating layer (the solid electrolyte interphase, or SEI) to form on the electrode surface, blocking Ca diffusion and preventing reversible plating and stripping of the Ca anode. In this work we use density functional theory (DFT) and ab initio molecular dynamics (AIMD) calculations to study the interaction of these solvents, including ethylene carbonate (EC), propylene carbonate (PC), and tetrahydrofuran (THF), with Ca ions and investigate their breakdown on the anode surface. [1,2] We find that Ca forms a large first solvation shell with EC and PC and a slightly smaller one in THF. We then compute the diffusion coefficient of Ca in each solvent using AIMD, and find that it diffuses fastest in THF, and slower in EC and PC. Finally, we use AIMD to study the decomposition of EC on Li, Ca, and Al surfaces and identify the principle components of the SEI on each. |
Monday, March 2, 2020 1:15PM - 1:27PM |
B21.00011: Proton conductivity mechanism of liquid imidazole - an ab initio molecular dynamics study Zhuoran Long, Austin Atsango, Joe Anthony Napoli, Thomas E Markland, Mark E Tuckerman Imidazole, as a fundamental organic compound, exhibits high proton conductivity comparable to water at similar temperatures relative to the melting point. Its potential application in fuel cells has motivated numerous experimental research efforts. However, details of the proton conductivity mechanism are still ambiguous. Using multiple time-step ab initio molecular dynamics simulations, we were able to accumulate trajectories totaling 1 ns in length. The predicted proton diffusion coefficient of imidazolium is 0.52 Å2/ps at 384K, and structural diffusion is the dominant mechanism. The proton transfer event is local and must go through a geometrically restricted Zundel-type transition state at a sub-picosecond time scale. Long hydrogen-bonded chains were detected in our liquid imidazole system within which the imidazolium defect undergoes frequent identity changes from individual proton transfer events. Chain diffusion is controlled by the dynamic hydrogen bond forming and breaking via rotational reorientation at a time scale of ~30ps. The decoupling of local proton transfer and chain diffusion together explains the fast proton hopping rate and relatively large diffusion coefficient of the charge defect. |
Monday, March 2, 2020 1:27PM - 1:39PM |
B21.00012: Smart power system: Tuning energy storage by electrophoretic repositioning of TiO2 nanoparticles in electrolytes. Biplav Acharya, Caitlin M Seed, Jacqueline Krim An effective strategy for efficient use of power is to deliver variable energy whose level depends on the fluctuating demand. Electric double layer capacitors are regarded as one approach suitable for such power management systems. Prior investigations of TiO2 nanomaterials have primarily focused on how they can be incorporated into a system’s electrodes and not its electrolytes. We demonstrate here that TiO2 nanoparticles (NPs) dispersed directly into an electrolyte may also be an approach to smart energy storage applications. Cyclic voltammetry measurements are employed to explore charge storage capabilities and, together with repositioning of the TiO2 and Al2O3 NPs in the electrolyte. TiO2 NPs are revealed to be actively positioned to form a transient film on the electrode surface, significantly enhancing the system’s energy storage capabilities. In contrast, minimal enhancement is observed for the Al2O3. This study shows that TiO2 NPs are intrinsically capable of being a component of a “smart power” system, designed to deliver variable power commensurate with a fluctuating demand. |
Monday, March 2, 2020 1:39PM - 1:51PM |
B21.00013: Ab Initio Study of the Discharge Mechanism of Bi- and Cu- Modified MnO2/Zn Rechargeable Batteries. Birendra Ale Magar, Nirajan Paudel, Timothy N. Lambert, Igor Vasiliev Bi and Cu additives have a great influence on the performance of rechargeable Zn/MnO2 batteries, however, the mechanism by which these additives affect the rechargeability and cyclability of the MnO2 electrode has not been explained in detail. We applied first-principles computational methods based on density functional theory to study the discharge mechanism of Bi- and Cu-modified δ-MnO2 electrodes in rechargeable Zn/MnO2 batteries. Our calculations show the possibility of formation of Bi-Mn and Cu-Mn oxides in Bi/Cu-modified δ-MnO2 cathodes during battery cycling. The results of our study suggest that the formation of intermediate Bi-Mn and Cu-Mn oxides could reduce the rate of accumulation of irreversible redox reaction products in the MnO2 electrode. |
Monday, March 2, 2020 1:51PM - 2:03PM |
B21.00014: Ab initio Analysis of Membrane Stability in Alkaline Environments: a Joint Density Functional Theory (JDFT) Study Mariel Tader, Wei You, Geoffrey Coates, Tomas Alberto Arias Improving membrane stability in alkaline environments is crucial to the development of alkaline fuel cells (AFCs). Ab initio studies using the nudged elastic band (NEB) method, combined with a detailed transition-state theory analysis, allow us not only to predict quantitative lifetimes of alkali-stable membrane polymers, but also to uncover unexpected mechanisms for improving membrane lifetime. In this later regard, we find that the choice of a first-principles joint-density functional theory (JDFT) description of the solvent and consideration of the impact of the hydrophobic regions of the membrane are critical to understanding the polymer degradation process. This work is foundational to computation-enabled searches for yet more stable AFC membranes. |
Monday, March 2, 2020 2:03PM - 2:15PM |
B21.00015: Enhancement of Quaternized Ammonium Polyaromatic Anion Membrane Performance in Alkaline Fuel Cells by Deposition of Graphene Oxide and Catalyst Ink Optimization Avinash Rao, Michael Han, Carter Bian, Miriam Rafailovich, Stoyan Bliznakov To bolster the performance of polyaromatic ionomer membranes in alkaline fuel cells (AFCs), two major modifications were made. First, catalyst ink composition was optimized to yield the maximum power performance for the low platinum loading (0.6 mg/cm2). From the tested compositions, an 80:20 (catalyst: ionomer) ratio produced the greatest results for quaternary ammonium biphenyl membranes, yielding an improved 66 mW/cm2 power density despite reduced back-pressure. |
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