Bulletin of the American Physical Society
APS March Meeting 2017
Volume 62, Number 4
Monday–Friday, March 13–17, 2017; New Orleans, Louisiana
Session L38: Li-ion Batteries: Advanced Characterization and Modeling |
Hide Abstracts |
Sponsoring Units: GERA Chair: Ilkyu Lee, Stanford University Room: 385 |
Wednesday, March 15, 2017 11:15AM - 11:27AM |
L38.00001: Numerical Study of X-ray Spectroscopies for Understanding Anionic Redox in Li-ion Battery Compounds through Charge Transfer Hybridization Full Atomic Multiplet Theory Ilkyu Lee, Chunjing Jia, Yvonne Kung, Brian Moritz, Tom Devereaux The field of rechargeable batteries has gained incredible attention due to Lithium-ion transition metal compounds and their attractive properties such as high energy density and low self-discharge. Although the discovery of an anionic redox center in addition to the usual cationic redox led to a greater understanding of these battery compounds, the mechanism behind the anionic redox still remains unclear with various possible explanations. In this study, we utilize a first-principles approach combined with full charge transfer and atomic multiplet model to investigate different models of anionic redox by simulating x-ray spectra for Li-ion battery compounds. Through comparison with existing experimental data, we aim to achieve a greater understanding of the anionic redox process, in hopes of controlling the process and predicting novel, better performing Li-ion compounds. [Preview Abstract] |
Wednesday, March 15, 2017 11:27AM - 11:39AM |
L38.00002: Visualizing redox orbitals and their potentials in olivine materials for advanced lithium-ion batteries Hasnain Hafiz, K. Suzuki, B. Barbiellini, Y. Orikasa, V. Callewaert, S. Kaprzyk, M. Itou, K. Yamamoto, R. Yamada, Y. Uchimoto, Y. Sakurai, H. Sakurai, A. Bansil The key reactions that take place in lithium batteries are reduction-oxidation (redox) reactions, which involve transfer of conduction electrons from the lithium anode to an orbital of the cathode. Our study of high-energy x-ray Compton scattering spectroscopy on olivine lithium iron phosphate $(LiFePO_{4})$ shows that inelastic scattering spectra of high-energy photons yield faithful reconstructions of the redox orbitals. The knowledge of the redox orbital-momentum distribution allows the extraction of information related to kinetic energies involved in the redox reactions and the visualization of trends in the voltage. Our results demonstrate that x-ray Compton scattering spectroscopy provides unique descriptors for monitoring fundamental quantum mechanical effects determining the battery voltage in olivine materials. [Preview Abstract] |
Wednesday, March 15, 2017 11:39AM - 11:51AM |
L38.00003: Novel borate additives for lithium-ion battery cathode passivation investigated with hard x-ray photoelectron spectroscopy Stephanie Rivard, Benjamin Young, David Heskett, Yingnan Dong, Yongfeng Hu, Brett Lucht Cathodes presently used in industry-standard graphite-based Li-ion batteries will limit capacity improvements made on the anode side due to electrochemical limitations. The high voltage spinel cathode, LiNi$_{\mathrm{0.5}}$Mn$_{\mathrm{1.5}}$O$_{\mathrm{4}}$, may permit a higher 4.7 V operating potential and represents a significant step in the journey to developing higher capacity rechargeable batteries. Successful employment of the high voltage cathode will require attention paid to formation of the cathode electrolyte interphase (CEI), a passivation layer that grows on the electrode surface to prevent decomposition of the electrolyte material. Herein we present an investigation of three novel borate additives to the standard electrolyte (ethylene carbonate/ethyl methyl carbonate solvent with LiPF$_{\mathrm{6}}$ salt) using Hard X-Ray Photoelectron Spectroscopy (HAXPES). Electrochemical cycling data reveal that the standard electrolyte is significantly outperformed by batteries with these additives at elevated temperature. The HAXPES data suggest that this may be due, in part, to the thickness of the CEI layer developed on each cathode, which we have approximated for each battery. Furthermore, we see evidence of additive decomposition on the better-performing batteries, which likely leads to more effective electrode passivation. [Preview Abstract] |
Wednesday, March 15, 2017 11:51AM - 12:03PM |
L38.00004: Identifying a descriptor for d-orbital delocalization in cathodes of Li batteries based on x-ray Compton scattering B. Barbiellini, K. Suzuki, Y. Orikasa, S. Kaprzyk, M. Itou, K. Yamamoto, Yung Jui Wang, H. Hafiz, R. Yamada, Y. Uchimoto, A. Bansil, Y. Sakurai, H. Sakurai We discuss how x-ray Compton scattering spectra can be used for investigating the evolution of electronic states in cathode materials of Li batteries under the lithiation/delithiation process. In particular, our analysis of the Compton spectra taken from polycrystalline Li$_x$CoO$_2$ samples shows that the spectra are dominated by the contribution of the O $2p$ redox orbital. We identify a distinct signature of Co $3d$ orbital delocalization, which is tied directly to the conductivity of the material, providing a descriptor [1] based on Compton spectra for monitoring the lithiation range with improved conductivity and kinetics for electrochemical operation. Our study demonstrates that Compton scattering spectroscopy can provide a window for probing complex electronic mechanisms underlying the charging and discharging processes in Li-battery materials.\\ \\ $\mbox{[1] B. Barbiellini {\em et al.} Applied Physics Letters {\bf 109} , 073102 (2016)}$ [Preview Abstract] |
Wednesday, March 15, 2017 12:03PM - 12:15PM |
L38.00005: Toward better Li-ion batteries: hard x-ray photoelectron spectroscopy investigation of binder materials for Si-based anodes Benjamin Young, David Heskett, Cao Cuong Nguyen, Joseph Woicik, Brett Lucht From portable electronics to space exploration, the desire for more capable rechargeable batteries is driving a search for high capacity anodes. There is much interest in incorporating silicon as a partial or full replacement for the current graphite material in the most popular batteries because it could potentially hold much more charge. There is a significant challenge, however, in that storing so much more lithium in either electrode as the battery is charged and discharged as this causes an accompanying increase in the physical size fluctuation of the electrodes. Specifically, in the anode where this investigation focuses, the active material may experience a 300{\%} volume change between the charged and discharged state. This makes a long lifetime difficult to achieve because the passivation layer protecting the electrolyte material from decomposition is compromised upon each cycle. One approach to accommodating the large volumetric fluctuation without sacrificing lifetime is to find a better material to include in the anode substrate to act as a binder. Ideally, such a material would permit the anode to fluctuate without breaking. Polyvinylidene fluoride (PVdF) is not successful for silicon-based anodes and we present Hard X-ray photoelectron spectroscopy studies of batteries incorporating three alternatives. The alternative binders outperform the PVdF and we present possible explanations. [Preview Abstract] |
Wednesday, March 15, 2017 12:15PM - 12:27PM |
L38.00006: Transmission electron microscopy study investigating Li intercalation in tunnel structured $\zeta $-V$_{\mathrm{2}}$O$_{\mathrm{5}}$ nanowire Arijita Mukherjee, Hyun Deog Yoo, Gene Nolis, Justin Andrews, Sarbajit Banerjee, Jordi Cabana, Robert Klie Energy storage research has become quite relevant in recent years with the advent of smarter electronic devices and electric vehicles that demand more efficient options. Orthorhombic $\alpha $-V$_{\mathrm{2}}$O$_{\mathrm{5\thinspace }}$has been known as a versatile intercalation cathode host for lithium and beyond Li cations, such as Na and Mg. Recent reports have established that a novel tunnel structured polymorph, $\zeta $-V$_{\mathrm{2}}$O$_{\mathrm{5}}$ can perform better as a cathode material, and can intercalate Li and Mg chemically. This contribution will focus on an in depth study of phase formation upon electrochemical Li intercalation of this new polymorph, $\zeta $-V$_{\mathrm{2}}$O$_{\mathrm{5}}$ using aberration corrected scanning transmission electron microscopy(STEM) electron energy loss spectroscopy(EELS) and energy dispersive X ray spectroscopy(EDX). Results will also be presented investigating Mg and Na intercalation into this $\zeta $-V$_{\mathrm{2}}$O$_{\mathrm{5\thinspace }}$polymorph and compare the electrochemical performance in the various scenarios directly with structural changes at an atomic scale. [Preview Abstract] |
Wednesday, March 15, 2017 12:27PM - 12:39PM |
L38.00007: Local Lithiation via Nanobattery Probes: Battery Interfaces at the Nanoscale Jonathan Larson, Alec Talin, Alexander Pearse, Janice Reutt-Robey Greater knowledge of interfacial charge/mass transport processes in battery materials - especially as a function of lithiation - is essential to understand and overcome materials limitations in performance. Increased use of nanostructured and/or nanoscale electrodes in energy storage systems, calls for research tools that allow for direct, local probes of materials interfaces and inhomogeneity. Here we present a new approach to measure local interfacial structure, electronics, and electrochemical properties as a function of local chemical changes, like lithiation. Building upon our laboratory's recent success in developing scanning probe techniques for energy storage science [1], we introduce novel probes layered with nanothin, functional energy-storage materials. We perform in situ measurements of the electronic properties of oxide-clad probes, via electron tunneling spectroscopy, determining effective electron transport gaps. We then utilize these probes as fine Li sources and as nanobattery probes for local cycling against a silicon anode substrate. Post lithiation, conventional in-situ STM and SEM reveal local physical changes in the cycled Si(111) anode surface. [1] J.M. Larson et al, Small, 2015, DOI: 10.1002/smll.201500999 [Preview Abstract] |
Wednesday, March 15, 2017 12:39PM - 12:51PM |
L38.00008: Influence of Valance and Magnetism on the Jahn-Teller Distortion in LiMn2O4 and its Lithiation Process Weiwei Liu, Yanning Zhang We performed extensive first-principles studies on the valence and magnetic configurations of spinel LiMn$_{2}$O$_{4}$, a promising candidate of cathode materials in Li-ion batteries. We find that the ground state of LiMn$_{2}$O$_{4}$ is an anti-ferromagnetic (AFM) orthorhombic spinel structure, where AFM Mn$^{3+}$ layer and FM Mn$^{4+}$ layer alternate along the [001] direction and the 90°Mn$^{3+}$-O$^{2-}$-Mn$^{3+}$ in Mn$^{3+}$-(001) planes is in AFM coupling, forming the indirect Kramers-Anderson superexchange. The coplanar Jahn-Teller (JT) ions maximize the JT distortion and the AFM magnetic orderings further strengthen the interaction between Mn$^{3+}$ cations and O$^{2-}$ anions, making the structure stable. Li diffusion in such a stable LiMn$_{2}$O$_{4}$ will go through a ring consisting of six Mn atoms, and the energy barrier of Li diffusion is dependent on the valence states of Mn atoms. Our theoretical results give insights in exploring ground state of related JT magnetic materials, and also provide information for the performance improvement of LiMn$_{2}$O$_{4}$ cathode materials. [Preview Abstract] |
Wednesday, March 15, 2017 12:51PM - 1:03PM |
L38.00009: Structure, morphology and stability of layered Li(Ni$_{\mathrm{1/3}}$Mn$_{\mathrm{1/3}}$Co$_{\mathrm{1/3}})$O$_{\mathrm{2}}$ surfaces Juan Garcia, Javier Bareno, Guoying Chen, Jason Croy, Hakim Iddir Energy storage devices with high energy densities are needed in order to meet the increasing demands of portable electronics and electric vehicles. Layered Li(Ni$_{\mathrm{1-x-y}}$Mn$_{\mathrm{x}}$Co$_{\mathrm{y}})$O$_{\mathrm{2}}$ (NMC) oxides are promising cathode materials that are capable of meeting many of these demands. However, in order to take advantage of these high intrinsic energies, charging voltages of \textgreater 4.2V (vs. graphite) are necessary. At such high voltages, surface degradation phenomena take place at untenable rates, thereby reducing the lifetime of cells. In order to take advantage of NMC-based Li-ion cells, the mechanisms of these surface degradation processes must be fully understood. This presentation will explore recent Density Functional Theory (DFT) efforts at Argonne National Laboratory aimed at predicting the stability of several low-index surfaces of Li(Ni$_{\mathrm{1/3}}$Mn$_{\mathrm{1/3}}$Co$_{\mathrm{1/3}})$O$_{\mathrm{2}}$ (NMC-111) as a function of Li and O chemical potentials. Comparison will be made of predicted particle shapes with those of single-crystal NMCs synthesized under different conditions. The most stable surfaces for stoichiometric NMC-111 will be discussed in terms of polar and non-polar surfaces as well as metal-oxygen bond breaking. The reactivity of these surfaces toward electrolyte oxidation will also be presented. [Preview Abstract] |
Wednesday, March 15, 2017 1:03PM - 1:15PM |
L38.00010: First Principles Modelling Insights into Lithium-Ion Battery Materials including Point Defects. Andrew Morris, Clare Grey, Chris Pickard, Martin Mayo, Kent Griffith The traditional lithium-ion battery(LIB) anode is composed of graphite but recently silicon has been proposed as an alternative due to its ten-fold increase in theoretical capacity. Using AIRSS[1] we have predicted phases of lithium group 4, group 5 and group 6 compounds[2,3,4] finding many new phases. We calculate average voltages, capacities and chemical shielding and compare these with in situ and ex situ NMR and XRD experiments[4,5]. Point-defect impurities can dramatically alter the properties of these materials. I show how using the defect-AIRSS technique we can obtain an insight into such processes in LIB, presenting some impurities which mitigate[6,7] and some which augment a battery's function[5].\\ 1. C.J. Pickard, and R.J. Needs, Phys. Rev. Lett. 97, 045504 (2006).\\ 2. A. J. Morris, C. P. Grey, C. J. Pickard, Phys. Rev. B 90, 054111, (2014).\\ 3. C. George, A. J. Morris, M. H. Modarres and M. De Volder, Chem. Mater. 28, 7304-7310, (2016).\\ 4. K. A See, et al., J. Am. Chem. Soc. 136 , 16368-16377, (2014).\\ 5. M. Mayo, K. J. Griffith, et al., Chem. Mater. 28, 2011, (2016).\\ 6. A. J. Morris, R. J. Needs, E. Salager, C. P. Grey and C. J. Pickard, Phys. Rev. B 87, 174108, (2013).\\ 7. K. Ogata, et al. Nature Comm. 5, 3217 (2014).\\ [Preview Abstract] |
Wednesday, March 15, 2017 1:15PM - 1:27PM |
L38.00011: Prediction of novel thermodynamically stable lithium-tin binary compounds at ambient and high pressure. Raja Sen, Priya Johari Volume expansion and elastic softening of Sn anode on lithiation result in mechanical degradation and pulverization of Sn, affecting the overall performance of Li-Sn batteries. It can however be overcome by using exotic high pressure quenched phases as prelithiated reagent. Under pressure many unusual stoichiometry which are basically impossible at ambient pressure, can be synthesized, which may even survive the decompression from high to ambient pressure. We therefore have performed first-principles evolutionary algorithm based simulations to explore the phase diagram of Li-Sn compounds in the pressure range of 1 atm-20 GPa. Besides the well-known existing Li-Sn compounds, our studies reveal the existence of five unreported stoichiometry (Li$_{8}$Sn$_{3}$, Li$_{3}$Sn$_{1}$, Li$_{4}$Sn$_{1}$, Li$_{5}$Sn$_{1}$, and Li$_{7}$Sn$_{1})$ at ambient and high pressure. While Li$_{8}$Sn$_{3}$ has been identified as one of the most stable Li-Sn compound in the entire pressure range, the pressure induced Li-rich compounds like Li$_{5}$Sn$_{1}$ and Li$_{7}$Sn$_{1}$ have been classified as providing higher theoretical gravimetric capacity of 1129 and 1580 mAhg$^{-1}$, respectively. [Preview Abstract] |
Wednesday, March 15, 2017 1:27PM - 1:39PM |
L38.00012: Insight into the limitation of intrinsic capacity of cathode materials for Li-ion batteries Peng Zhang, Wei Suhuai To increase the capacity of Li-ion batteries (LIBs), development of new cathode materials that can accommodate more than one Li ions per formula unit (f.u.) is highly required. However, one critical point is that the nominal amount of Li ions stored in cathode materials may not equal to their practical capacities, i.e. there may be a certain amount of inert Li ions that cannot be reversibly used. Based on the DFT calculations, we identify a general rule of intrinsic capacity limitation for LIB cathode materials, especially for those with more than one Li ions per f.u. in their hosts. Based on the rule, it is easy to understand why only one Li ion in many Li-rich cathode materials, e.g. Li$_{\mathrm{2}}$FeSiO$_{\mathrm{4}}$, could be reversibly used. Thus, this rule implies a guideline for future cathode design. [Preview Abstract] |
Wednesday, March 15, 2017 1:39PM - 1:51PM |
L38.00013: Mo2C as a high capacity anode material: a first-principles study Deniz Cakir, Cem Sevik, Oguz Gulseren, Francois Peeters The adsorption and diffusion of Li, Na, K and Ca atoms on a Mo2C monolayer are investigated by using first principles methods. We found that the considered metal atoms are strongly bound to the Mo2C monolayer. However, the adsorption energies of these alkali and earth alkali elements decreases as coverage increases due to the enhanced repulsion between the metal ions. We predict a significant charge transfer from the ad-atoms to the Mo2C monolayer, which indicates clearly the cationic state of the metal atoms. The metallic character of both pristine and doped Mo2C ensures a good electronic conduction. Low migration energy barriers are predicted as small as 43 meV for Li, 19 meV for Na and 15 meV for K, which result in the very fast diffusion of these atoms on Mo2C. For Mo2C, we found a store capacity larger than 400 mAh/g by the inclusion of multilayer adsorption. Mo2C expands slightly upon deposition of Li and Na even at high concentrations, which ensures a good cyclic stability of the atomic layer. The calculated average voltage of 0.68 V for Li and 0.30 V for Na ions makes Mo2C attractive for low charging voltage applications. D. Cak\i r, C. Sevik, O. Gulseren and F. M. Peeters, J. Mater. Chem. A 4, 6029 (2016). [Preview Abstract] |
Wednesday, March 15, 2017 1:51PM - 2:03PM |
L38.00014: The Effect of Oxidation and Charge/Discharge rates on Li Plating in All-Solid-State Batteries Alexander Yulaev, Vladimir Oleshko, A. Alec Talin, Marina S. Leite, Andrei Kolmakov All-solid-state Li-ion batteries (SSLIBs) is currently an extensive area of research due to their promising specific power and energy density properties. Moreover, SSLIBs significantly mitigate the safety risks of the thermal runaway that may occur in liquid electrolyte batteries. We fabricated a model SSLIB, which consists of LiCoO$_{\mathrm{2}}$ cathode layer, LiPON as an electrolyte, and a model ultra-thin carbon anode. Using in operando scanning electron microscopy in conjunction with electrochemical measurements, we found that depending on ambient oxidizing conditions and charging rate, the morphology of plated lithium alternates between quasi-1D and 3D microstructures. In addition, we were able to use an electron beam as a virtual nano-electrode to selectively control the nucleation rate and Li growth structure during the SSLIB charging with high spatial resolution. Finally, we determined the conditions when lithium may be oxidized even during battery cycling under UHV conditions, leading to significant capacity losses. We foresee that our work will provide deeper insights into a safe SSLIB performance under real world operating conditions. [Preview Abstract] |
Wednesday, March 15, 2017 2:03PM - 2:15PM |
L38.00015: Car-Parrinello molecular dynamics study of the charge-discharge cycle in lithium-ion battery materials Y. F. Kung, C.J. Jia, W. E. Gent, I. Lee, B. Moritz, T. P. Devereaux Lithium-ion transition metal oxide compounds have shown great potential for use as battery electrodes. However, the underlying structural modifications which accompany delithiation during battery charging remain less well understood. Formation of peroxide-like species and cation migration between layers comprise two promising candidates for describing numerous experimental observations. Taking Li$_2$RuO$_3$ as a model system, we use Car-Parrinello molecular dynamics to examine the structural changes that occur during delithiation and lithiation. We compare our results to existing experimental observations in other compounds and provide guidance for future experiments, including resonant inelastic x-ray scattering (RIXS). [Preview Abstract] |
Follow Us |
Engage
Become an APS Member |
My APS
Renew Membership |
Information for |
About APSThe American Physical Society (APS) is a non-profit membership organization working to advance the knowledge of physics. |
© 2024 American Physical Society
| All rights reserved | Terms of Use
| Contact Us
Headquarters
1 Physics Ellipse, College Park, MD 20740-3844
(301) 209-3200
Editorial Office
100 Motor Pkwy, Suite 110, Hauppauge, NY 11788
(631) 591-4000
Office of Public Affairs
529 14th St NW, Suite 1050, Washington, D.C. 20045-2001
(202) 662-8700