publications
Publications sorted in chronological order.
2023
- ACS Energy Lett.Removing the Two-Phase Transition in Spinel LiMn2O4 through Cation DisorderTina Chen, Julia Yang, Luis Barroso-Luque, and 1 more authorACS Energy Letters, Jan 2023
Resource constraints have become critical for the Li-ion industry. Spinel LiMn2O4 presents a cheaper, more sustainable alternative to traditional layered Li-ion cathodes, but its capacity is constrained by a two-phase transition at 3 V associated with large, inhomogeneous volume change leading to capacity loss. In this Letter, we argue that disorder can replace the two-phase region with solid-solution behavior to create high-capacity cathodes. By investigating the voltage curve and lithiation pathway of LiMn2O4 spinel with varying levels of Mn disorder, we find that disorder shortens the 3 V plateau by raising the energy landscape and stabilizing motifs found in solid-solution configurations. The plateau disappears completely with 25% Mn 16c occupancy. These results provide guidance on the optimal level of disorder in spinels to achieve both solid-solution behavior and good Li mobility and also highlight more generally how disorder can be utilized to reduce the effects of problematic phase transformations in ordered frameworks.
@article{chen_removing_2023, title = {Removing the {{Two-Phase Transition}} in {{Spinel LiMn2O4}} through {{Cation Disorder}}}, author = {Chen, Tina and Yang, Julia and {Barroso-Luque}, Luis and Ceder, Gerbrand}, year = {2023}, month = jan, journal = {ACS Energy Letters}, volume = {8}, number = {1}, pages = {314--319}, publisher = {{American Chemical Society}}, doi = {10.1021/acsenergylett.2c02141} } - Semigrand-Canonical Monte-Carlo Simulation Methods for Charge-Decorated Cluster ExpansionsFengyu Xie, Peichen Zhong, Luis Barroso-Luque, and 2 more authorsComputational Materials Science, Feb 2023
Monte-Carlo sampling of lattice model Hamiltonians is a well-established technique in statistical mechanics for studying the configurational entropy of crystalline materials. When the species to be distributed on the lattice carry charge, the charge balance constraint on the overall system prohibits single-site Metropolis exchanges in MC. In this article, we propose two methods to perform MC sampling in the semigrand-canonical ensemble in the presence of a charge-balance constraint. The table-exchange method (TE) constructs small charge-conserving excitations, and the square-charge bias method (SCB) allows the system to temporarily drift away from charge neutrality. We illustrate the effect of internal hyper-parameters on the efficiency of these algorithms and suggest practical strategies on how to employ these algorithms in real applications.
@article{xie_semigrand-canonical_2023, title = {Semigrand-Canonical {{Monte-Carlo}} Simulation Methods for Charge-Decorated Cluster Expansions}, author = {Xie, Fengyu and Zhong, Peichen and {Barroso-Luque}, Luis and Ouyang, Bin and Ceder, Gerbrand}, year = {2023}, month = feb, journal = {Computational Materials Science}, volume = {218}, pages = {112000}, issn = {0927-0256}, doi = {10.1016/j.commatsci.2022.112000} } - Ab Initio Study of Short-Range Ordering in Vanadium-Based Disordered Rocksalt StructuresZinab Jadidi, Julia H. Yang, Tina Chen, and 2 more authorsJournal of Materials Chemistry A, Jul 2023
Disordered rocksalt Li-excess (DRX) compounds are attractive new cathode materials for Li-ion batteries as they contain resource-abundant metals and do not require the use of cobalt or nickel. Understanding the delithiation process and cation short-range ordering (SRO) in DRX compounds is essential to improve these promising cathode materials. Herein, we use first-principles calculations along with the cluster-expansion approach to model the disorder in DRX Li2−xVO3, 0 < x < 1. We discuss the SRO of Li in tetrahedral and octahedral sites, and the order in which Li delithiates and V oxidizes with respect to local environments. We reveal that the number of nearest-neighbor V dictates the order of delithiation from octahedral sites and that V is oxidized in a manner that minimizes the electrostatic interactions among V. Our results provide valuable insight for tailoring the performance of V-based DRX cathode materials in general by controlling the SRO features that reduce energy density.
@article{jadidi_ab_2023, title = {Ab Initio Study of Short-Range Ordering in Vanadium-Based Disordered Rocksalt Structures}, author = {Jadidi, Zinab and Yang, Julia H. and Chen, Tina and Barroso-Luque, Luis and Ceder, Gerbrand}, year = {2023}, month = jul, journal = {Journal of Materials Chemistry A}, volume = {11}, number = {33}, pages = {17728--17736}, publisher = {{The Royal Society of Chemistry}}, issn = {2050-7496}, doi = {10.1039/D3TA02475J} } - Modeling Intercalation Chemistry with Multiredox Reactions by Sparse Lattice Models in Disordered Rocksalt CathodesPeichen Zhong, Fengyu Xie, Luis Barroso-Luque, and 2 more authorsPRX Energy, Oct 2023
Modern battery materials can contain many elements with substantial site disorder, and their configurational state has been shown to be critical for their performance. The intercalation voltage profile is a critical parameter to evaluate the performance of energy storage. The application of commonly used cluster expansion techniques to model the intercalation thermodynamics of such systems ab initio is challenged by the combinatorial increase in configurational degrees of freedom as the number of species grows. Such challenges necessitate the efficient generation of lattice models without overfitting and proper sampling of the configurational space under the requirement of charge balance in ionic systems. In this work, we introduce a combined approach that addresses these challenges by (1) constructing a robust cluster expansion Hamiltonian using the sparse regression technique, including ℓ0ℓ2-norm regularization and structural hierarchy; and (2) implementing semigrand-canonical Monte Carlo to sample charge-balanced ionic configurations using the table-exchange method and an ensemble average approach. These techniques are applied to a disordered rocksalt oxyfluoride Li1.3−xMn0.4Nb0.3O1.6F0.4 (LMNOF) that is part of a family of promising earth-abundant cathode materials. The simulated voltage profile is found to be in good agreement with experimental data and particularly provides a clear demonstration of the Mn and oxygen contributions to the redox potential as a function of Li content.
@article{zhong_modeling_2023, title = {Modeling {{Intercalation Chemistry}} with {{Multiredox Reactions}} by {{Sparse Lattice Models}} in {{Disordered Rocksalt Cathodes}}}, author = {Zhong, Peichen and Xie, Fengyu and Barroso-Luque, Luis and Huang, Liliang and Ceder, Gerbrand}, year = {2023}, month = oct, journal = {PRX Energy}, volume = {2}, number = {4}, pages = {043005}, publisher = {{American Physical Society}}, doi = {10.1103/PRXEnergy.2.043005} } - Kinetics of Li Transport in Vanadium-Based Disordered Rocksalt StructuresZinab Jadidi, Tina Chen, Luis Barroso-Luque, and 1 more authorChemistry of Materials, Oct 2023
Disordered rocksalt Li-excess (DRX) compounds have emerged as promising new cathode materials for lithium-ion batteries, as they can consist solely of resource-abundant metals and eliminate the need for cobalt or nickel. A deeper understanding of the lithium-ion transport kinetics in DRX compounds is essential for enhancing their rate performance. This study employs first-principles calculations, cluster expansion techniques, and kinetic Monte Carlo simulations to investigate the Li+ transport properties in DRX Li2–xVO3, where 0 ≤ x ≤ 1. Our findings underscore (i) the necessity of accounting for both tetrahedral and octahedral Li occupancy when predicting the transport properties in DRX materials, (ii) the factors influencing the variation in the diffusion coefficients with Li content in Li2–xVO3, and (iii) the impact of Li+ correlated motion on the kinetics of Li+ transport. We reveal that the relative stability of tetrahedral and octahedral Li determines the number of active sites within the percolation network, subsequently affecting the Li+ transport properties. Furthermore, we demonstrate that the wide site energy distribution causes correlated motion in Li2–xVO3, which hinders Li+ transport.
@article{jadidi_kinetics_2023, title = {Kinetics of {{Li Transport}} in {{Vanadium-Based Disordered Rocksalt Structures}}}, author = {Jadidi, Zinab and Chen, Tina and Barroso-Luque, Luis and Ceder, Gerbrand}, year = {2023}, month = oct, journal = {Chemistry of Materials}, publisher = {{American Chemical Society}}, issn = {0897-4756}, doi = {10.1021/acs.chemmater.3c01941} } - Crystal Structures and Phase Stability of the Li2S–P2S5 System from First PrinciplesRonald L. Kam, KyuJung Jun, Luis Barroso-Luque, and 3 more authorsChemistry of Materials, Oct 2023
The Li2S–P2S5 pseudo-binary system has been a valuable source of promising superionic conductors, with α-Li3PS4, β-Li3PS4, HT-Li7PS6, and Li7P3S11 having excellent room-temperature Li-ion conductivity >0.1 mS/cm. The metastability of these phases at ambient temperature motivates a study to quantify their thermodynamic accessibility. Through calculating the electronic, configurational, and vibrational sources of free energy from first principles, a phase diagram of the crystalline Li2S–P2S5 space is constructed. New ground-state orderings are proposed for α-Li3PS4, HT-Li7PS6, LT-Li7PS6, and Li7P3S11. Well-established phase stability trends from experiments are recovered, such as polymorphic phase transitions in Li7PS6 and Li3PS4, and the instability of Li7P3S11 at high temperature. At ambient temperature, it is predicted that all superionic conductors in this space are indeed metastable but thermodynamically accessible. Vibrational and configurational sources of entropy are shown to be essential toward describing the stability of superionic conductors. New details of the Li sublattices are revealed and are found to be crucial toward accurately predicting configurational entropy. All superionic conductors contain significant configurational entropy, which suggests an inherent correlation between fast Li diffusion and thermodynamic stability arising from the configurational disorder.
@article{kam_crystal_2023-1, title = {Crystal {{Structures}} and {{Phase Stability}} of the {{Li2S}}\textendash{{P2S5 System}} from {{First Principles}}}, author = {Kam, Ronald L. and Jun, KyuJung and Barroso-Luque, Luis and Yang, Julia H. and Xie, Fengyu and Ceder, Gerbrand}, year = {2023}, month = oct, journal = {Chemistry of Materials}, publisher = {{American Chemical Society}}, issn = {0897-4756}, doi = {10.1021/acs.chemmater.3c01793} }
2022
- Approaches for handling high-dimensional cluster expansions of ionic systemsJulia H. Yang, Tina Chen, Luis Barroso-Luque, and 2 more authorsnpj Computational Materials, Jun 2022
Disordered multicomponent systems attract great interest due to their engineering design flexibility and subsequent rich space of properties. However, detailed characterization of the structure and atomic correlations remains challenging and hinders full navigation of these complex spaces. A lattice cluster expansion is one tool to obtain configurational and energetic resolution. While in theory a cluster expansion can be applied to any system of any dimensionality, the method has primarily been used in binary systems or ternary alloys. Here we apply cluster expansions in high-component ionic systems, setting up the largest cluster expansion ever attempted to our knowledge. In doing so, we address and discuss challenges specific to high-component ionic systems, namely charge state assignments, structural relaxations, and rank-deficient systems. We introduce practical procedures to make the fitting and analysis of complex systems tractable, providing guidance for future computational studies of disordered ionic systems.
@article{yang_approaches_2022, title = {Approaches for handling high-dimensional cluster expansions of ionic systems}, author = {Yang, Julia H. and Chen, Tina and {Barroso-Luque}, Luis and Jadidi, Zinab and Ceder, Gerbrand}, year = {2022}, month = jun, journal = {npj Computational Materials}, volume = {8}, number = {1}, pages = {1--11}, publisher = {{Nature Publishing Group}}, doi = {10.1038/s41524-022-00818-3} } - An l0l2-norm regularized regression model for construction of robust cluster expansions in multicomponent systemsPeichen Zhong, Tina Chen, Luis Barroso-Luque, and 2 more authorsPhysical Review B, Jul 2022
We introduce \ell_0\ell_2-norm regularization and hierarchy constraints into linear regression for the construction of cluster expansions to describe configurational disorder in materials. The approach is implemented through mixed integer quadratic programming (MIQP). The ℓ2-norm regularization is used to suppress intrinsic data noise, while the ℓ0-norm is used to penalize the number of nonzero elements in the solution. The hierarchy relation between clusters imposes relevant physics and is naturally included by the MIQP paradigm. As such, sparseness and cluster hierarchy can be well optimized to obtain a robust, converged set of effective cluster interactions with improved physical meaning. We demonstrate the effectiveness of ℓ0ℓ2-norm regularization in two high-component disordered rocksalt cathode material systems, where we compare the cross-validation, convergence speed, and the reproduction of phase diagrams, voltage profiles, and Li-occupancy energies with those of the conventional ℓ1-norm regularized cluster expansion models.
@article{zhong_l02-norm_2022, author = {Zhong, Peichen and Chen, Tina and {Barroso-Luque}, Luis and Xie, Fengyu and Ceder, Gerbrand}, year = {2022}, month = jul, journal = {Physical Review B}, volume = {106}, number = {2}, pages = {024203}, publisher = {{American Physical Society}}, doi = {10.1103/PhysRevB.106.024203}, title = {An l0l2-norm regularized regression model for construction of robust cluster expansions in multicomponent systems} } - smol: A Python package for cluster expansions and beyondLuis Barroso-Luque, Julia H. Yang, Fengyu Xie, and 5 more authorsJournal of Open Source Software, Sep 2022
@article{barroso-luque_smol_2022, title = {smol: {{A Python}} package for cluster expansions and beyond}, shorttitle = {smol}, author = {{Barroso-Luque}, Luis and Yang, Julia H. and Xie, Fengyu and Chen, Tina and Kam, Ronald L. and Jadidi, Zinab and Zhong, Peichen and Ceder, Gerbrand}, year = {2022}, month = sep, journal = {Journal of Open Source Software}, volume = {7}, number = {77}, pages = {4504}, issn = {2475-9066}, doi = {10.21105/joss.04504} } - Cluster expansions of multicomponent ionic materials: Formalism and methodologyLuis Barroso-Luque, Peichen Zhong, Julia H. Yang, and 4 more authorsPhysical Review B, Oct 2022
The cluster expansion (CE) method has seen continuous and increasing use in the study of configuration-dependent properties of crystalline materials. The original development of the CE method along with the underlying mathematical formalism and assumptions was focused on the study of metallic alloys. Since then the methodology has been actively and successfully used in the study of ionic materials as well. In this work, we present a cohesive reformulation of the mathematical formalism underlying the CE method based on a synthesis of its original formulation, several additions and extensions that have been proposed since, and a revised representation of its constituent mathematical objects. We then proceed to describe some of the formal implications of using the methodology for charge-neutral configurations in ionic systems. In particular, we discuss the reduction of the size of configuration spaces and the resulting linear dependencies that arise among correlation functions that span the larger unconstrained configuration space. Additionally, we explore the effects of long-range electrostatic interactions. We also demonstrate how the previously proposed use of a point electrostatic term successfully accounts for the majority of the longer-range electrostatic interactions, and leaves the cluster expansion terms to capture mostly short-range interactions. Finally, we present and discuss a variety of recently developed methodologies, including training structure selection, oxidation state assignment, structure mapping, and regression algorithms, that are necessary to address these formal mathematical notions for a practical implementation of the CE method in the study of multicomponent ionic materials.
@article{barroso-luque_cluster_2022, title = {Cluster expansions of multicomponent ionic materials: {{Formalism}} and methodology}, shorttitle = {Cluster expansions of multicomponent ionic materials}, author = {{Barroso-Luque}, Luis and Zhong, Peichen and Yang, Julia H. and Xie, Fengyu and Chen, Tina and Ouyang, Bin and Ceder, Gerbrand}, year = {2022}, month = oct, journal = {Physical Review B}, volume = {106}, number = {14}, pages = {144202}, publisher = {{American Physical Society}}, doi = {10.1103/PhysRevB.106.144202} }
2021
- Sparse expansions of multicomponent oxide configuration energy using coherency and redundancyLuis Barroso-Luque, Julia H. Yang, and Gerbrand CederPhysical Review B, Dec 2021
Compressed sensing has become a widely accepted paradigm to construct high dimensional cluster expansion models used for statistical mechanical studies of atomic configuration in complex multicomponent crystalline materials. However, strict sampling requirements necessary to obtain minimal coherence measurements for compressed sensing to guarantee accurate estimation of model parameters are difficult and in some cases impossible to satisfy due to the inability of physical systems to access certain configurations. Nevertheless, the dependence of energy on atomic configuration can still be adequately learned without these strict requirements by using compressed sensing by way of coherent measurements using redundant function sets known as frames. We develop a particular frame constructed from the union of all occupancy-based cluster expansion basis sets. We illustrate how using this highly redundant frame yields sparse expansions of the configuration energy of complex oxide materials that are competitive and often surpass the prediction accuracy and sparsity of models obtained from standard cluster expansions.
@article{barroso-luque_sparse_2021, title = {Sparse expansions of multicomponent oxide configuration energy using coherency and redundancy}, author = {{Barroso-Luque}, Luis and Yang, Julia H. and Ceder, Gerbrand}, year = {2021}, month = dec, journal = {Physical Review B}, volume = {104}, number = {22}, pages = {224203}, publisher = {{American Physical Society}}, doi = {10.1103/PhysRevB.104.224203} }
2020
- An analysis of solid-state electrodeposition-induced metal plastic flow and predictions of stress states in solid ionic conductor defectsLuis Barroso-Luque, Qingsong Tu, and Gerbrand CederJournal of the Electrochemical Society, Jan 2020
The use of inorganic solid-ionic conductors with a metal electrode, has been proposed as a way to increase energy density, decrease capacity loss and prevent failure from metal propagation. Current observations of Li-metal electrodes causing cell shorting in solid-state systems have been identified as main obstacles limiting the development of this technology. However, many aspects of the involved phenomenon have not been fully addressed theoretically. In this work, we derive a mathematical model of electrodeposition-induced plastic flow in metal/inorganic solid-conductor systems. We use a semi-analytical solution to derive pressure increase expressions at metal protrusions and assess the possibility of fracture. The results give flow solutions analogous to laminar channel flow. The solutions also show how taking into account a boundary traction potential from built up pressure, leads to ionic redistribution and effectively screens isolated flaws, making local current focusing an incomplete explanation for observed electrolyte fracture. We show that the boundary traction potential sets a maximum value for the pressure increase that can occur from deposition at an isolated flaw. We derive conditions under which fracture can occur, and quantify the role of ionic conductivity and electrolyte fracture toughness in extending safe operating regimes of solid-state electrolytes with metal electrodes.
@article{barroso-luque_analysis_2020, title = {An analysis of solid-state electrodeposition-induced metal plastic flow and predictions of stress states in solid ionic conductor defects}, author = {{Barroso-Luque}, Luis and Tu, Qingsong and Ceder, Gerbrand}, year = {2020}, month = jan, volume = {167}, number = {2}, pages = {020534}, journal = {Journal of the Electrochemical Society}, publisher = {{The Electrochemical Society}}, doi = {10.1149/1945-7111/ab6c5b} } - Electrodeposition and mechanical stability at lithium-solid electrolyte interface during plating in solid-state batteriesQingsong Tu, Luis Barroso-Luque, Tan Shi, and 1 more authorCell Reports Physical Science, Jul 2020
Interfacial deposition stability between lithium metal and a solid electrolyte (SE) is important in preventing interfacial contact loss, mechanical fracture, and dendrite growth in Li-metal solid-state batteries (SSBs). In this work, we investigate the deposition and mechanical stability at the Li-metal/SE interface and its consequences (such as SE fracture and contact loss). A wide range of contributing factors are investigated, such as charge and mass transfer kinetics, plasticity of Li-metal and fracture of the SE, and the applied stack pressure. We quantify the effect of the ionic conductivity of the SE, the exchange current density of the interfacial charge-transfer reaction, and SE surface roughness on the Li deposition stability at the Li-metal/SE interface. We also propose a “mechanical stability window” for the applied stack pressure that can prevent both contact loss and SE fracture, which can be extended to other metal-electrode (e.g., sodium) SSB systems.
@article{tu_electrodeposition_2020, title = {Electrodeposition and mechanical stability at lithium-solid electrolyte interface during plating in solid-state batteries}, author = {Tu, Qingsong and {Barroso-Luque}, Luis and Shi, Tan and Ceder, Gerbrand}, year = {2020}, month = jul, journal = {Cell Reports Physical Science}, volume = {1}, number = {7}, pages = {100106}, doi = {10.1016/j.xcrp.2020.100106} }
2018
- Xi-Cam: A versatile interface for data visualization and analysisR. J. Pandolfi, D. B. Allan, E. Arenholz, and 34 more authorsJournal of Synchrotron Radiation, Jul 2018
Xi-cam is an extensible platform for data management, analysis and visualization. Xi-cam aims to provide a flexible and extensible approach to synchrotron data treatment as a solution to rising demands for high-volume/high-throughput processing pipelines. The core of Xi-cam is an extensible plugin-based graphical user interface platform which provides users with an interactive interface to processing algorithms. Plugins are available for SAXS/WAXS/GISAXS/GIWAXS, tomography and NEXAFS data. With Xi-cam’s ‘advanced’ mode, data processing steps are designed as a graph-based workflow, which can be executed live, locally or remotely. Remote execution utilizes high-performance computing or de-localized resources, allowing for the effective reduction of high-throughput data. Xi-cam’s plugin-based architecture targets cross-facility and cross-technique collaborative development, in support of multi-modal analysis. Xi-cam is open-source and cross-platform, and available for download on GitHub.
@article{pandolfi_xi-cam_2018, title = {Xi-Cam: A versatile interface for data visualization and analysis}, author = {Pandolfi, R. J. and Allan, D. B. and Arenholz, E. and {Barroso-Luque}, L. and Campbell, S. I. and Caswell, T. A. and Blair, A. and De Carlo, F. and Fackler, S. and Fournier, A. P. and Freychet, G. and Fukuto, M. and G{\"u}rsoy, D. and Jiang, Z. and Krishnan, H. and Kumar, D. and Kline, R. J. and Li, R. and Liman, C. and Marchesini, S. and Mehta, A. and N'Diaye, A. T. and Parkinson, D. Y. and Parks, H. and Pellouchoud, L. A. and Perciano, T. and Ren, F. and Sahoo, S. and Strzalka, J. and Sunday, D. and Tassone, C. J. and Ushizima, D. and Venkatakrishnan, S. and Yager, K. G. and Zwart, P. and Sethian, J. A. and Hexemer, A.}, year = {2018}, month = jul, journal = {Journal of Synchrotron Radiation}, volume = {25}, number = {4}, pages = {1261--1270}, publisher = {{International Union of Crystallography}}, doi = {10.1107/S1600577518005787} }