Understanding the Solid-State Electrode–Electrolyte Interface of a Model System Using First-Principles Statistical Mechanics and Thin-Film X-ray Characterization

Howard, Jason D.; Evmenenko, Guennadi; Kim, Jae Jin; Warburton, Robert E.; Patel, Shane; Fister, Timothy T.; Buchholz, D. Bruce; Greeley, Jeffrey; Curtiss, Larry A.; Fenter, Paul

doi:10.1021/acsami.1c20988

Title: Understanding the Solid-State Electrode–Electrolyte Interface of a Model System Using First-Principles Statistical Mechanics and Thin-Film X-ray Characterization

Journal Article · 28 January 2022 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.1c20988 · OSTI ID:1869002

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Argonne National Lab. (ANL), Lemont, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Purdue Univ., West Lafayette, IN (United States)
Northwestern Univ., Evanston, IL (United States). Materials Research Science and Engineering Center (MRSEC)

Intermixing of atomic species at the electrode-electrolyte boundaries can impact the properties of the interfaces in solid-state batteries. Herein, this work uses first-principles statistical mechanics along with experimental characterization to understand intermixing at the electrode-electrolyte interface. For the model presented in this work, lithium manganese oxide (LiMn₂O₄, LMO) and lithium lanthanum titanate (Li_3xLa_2/3-xTiO₃, LLTO) are employed as the cathode and electrolyte, respectively. The results of the computational work show that Ti-Mn intermixing at the interface is significant at synthesis temperatures. The experimental results in this work find that, at some critical temperatures between 600 and 700 degrees C for material preparation, the interface of LLTO-LMO becomes blurred. Calculations predict that the interface is unstable with regard to Ti-Mn intermixing starting at 0 K, suggesting that the critical temperature found in the experiment is related to kinetics. The work overall suggests that, in designing a solid-state battery, the fundamental reactions such as intermixing need to be considered.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1869002

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 5 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (50)

Origin of High Interfacial Resistances in Solid‐State Batteries: Interdiffusion and Amorphous Film Formation in Li _0.33 La _0.57 TiO ₃ /LiMn ₂ O ₄ Half Cells Xu, Pengyu; Rheinheimer, Wolfgang; Shuvo, Shoumya Nandy ChemElectroChem, Vol. 6, Issue 17 https://doi.org/10.1002/celc.201901068	journal	August 2019
Electronic properties of LiMn2−x Ti x O4 Song, Jie; Hong, Bing-Lin; Zheng, Jun Applied Physics A, Vol. 98, Issue 2 https://doi.org/10.1007/s00339-009-5420-y	journal	September 2009
Lithium insertion into manganese spinels Thackeray, M. M.; David, W. I. F.; Bruce, P. G. Materials Research Bulletin, Vol. 18, Issue 4, p. 461-472 https://doi.org/10.1016/0025-5408(83)90138-1	journal	April 1983
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Review on solid electrolytes for all-solid-state lithium-ion batteries Zheng, Feng; Kotobuki, Masashi; Song, Shufeng Journal of Power Sources, Vol. 389 https://doi.org/10.1016/j.jpowsour.2018.04.022	journal	June 2018
Hetero-epitaxial growth of Li0.17La0.61TiO3 solid electrolyte on LiMn2O4 electrode for all solid-state batteries Kim, Sangryun; Hirayama, Masaaki; Suzuki, Kota Solid State Ionics, Vol. 262 https://doi.org/10.1016/j.ssi.2013.09.040	journal	September 2014
Interphase formation on lithium solid electrolytes—An in situ approach to study interfacial reactions by photoelectron spectroscopy Wenzel, Sebastian; Leichtweiss, Thomas; Krüger, Dominik Solid State Ionics, Vol. 278 https://doi.org/10.1016/j.ssi.2015.06.001	journal	October 2015
Influence of composition on the structure and conductivity of the fast ionic conductors La2/3−xLi3xTiO3 (0.03≤x≤0.167) Ibarra, J. Solid State Ionics, Vol. 134, Issue 3-4 https://doi.org/10.1016/s0167-2738(00)00761-x	journal	October 2000
Electrochemical Nature of the Cathode Interface for a Solid-State Lithium-Ion Battery: Interface between LiCoO ₂ and Garnet-Li ₇ La ₃ Zr ₂ O ₁₂ Park, Kyusung; Yu, Byeong-Chul; Jung, Ji-Won Chemistry of Materials, Vol. 28, Issue 21 https://doi.org/10.1021/acs.chemmater.6b03870	journal	October 2016
Probing Solid–Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations Tang, Hanmei; Deng, Zhi; Lin, Zhuonan Chemistry of Materials, Vol. 30, Issue 1 https://doi.org/10.1021/acs.chemmater.7b04096	journal	December 2017
Interfaces and Interphases in All-Solid-State Batteries with Inorganic Solid Electrolytes Banerjee, Abhik; Wang, Xuefeng; Fang, Chengcheng Chemical Reviews, Vol. 120, Issue 14 https://doi.org/10.1021/acs.chemrev.0c00101	journal	June 2020
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis Chemical Reviews, Vol. 116, Issue 1 https://doi.org/10.1021/acs.chemrev.5b00563	journal	December 2015
Charged and Discharged States of Cathode/Sulfide Electrolyte Interfaces in All-Solid-State Lithium Ion Batteries Sumita, Masato; Tanaka, Yoshinori; Ikeda, Minoru The Journal of Physical Chemistry C, Vol. 120, Issue 25 https://doi.org/10.1021/acs.jpcc.6b01207	journal	June 2016
Strain-Driven Mn-Reorganization in Overlithiated Li _x Mn ₂ O ₄ Epitaxial Thin-Film Electrodes Chen, Xiao; Vörös, Márton; Garcia, Juan C. ACS Applied Energy Materials, Vol. 1, Issue 6 https://doi.org/10.1021/acsaem.8b00270	journal	May 2018
Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations Zhu, Yizhou; He, Xingfeng; Mo, Yifei ACS Applied Materials & Interfaces, Vol. 7, Issue 42 https://doi.org/10.1021/acsami.5b07517	journal	October 2015
Thermodynamic Stability of Low- and High-Index Spinel LiMn ₂ O ₄ Surface Terminations Warburton, Robert E.; Iddir, Hakim; Curtiss, Larry A. ACS Applied Materials & Interfaces, Vol. 8, Issue 17 https://doi.org/10.1021/acsami.6b01069	journal	April 2016
Cation Mixing Properties toward Co Diffusion at the LiCoO ₂ Cathode/Sulfide Electrolyte Interface in a Solid-State Battery Haruyama, Jun; Sodeyama, Keitaro; Tateyama, Yoshitaka ACS Applied Materials & Interfaces, Vol. 9, Issue 1 https://doi.org/10.1021/acsami.6b08435	journal	December 2016
Promising All-Solid-State Batteries for Future Electric Vehicles Sun, Yang-Kook ACS Energy Letters, Vol. 5, Issue 10 https://doi.org/10.1021/acsenergylett.0c01977	journal	October 2020
Understanding the Role of Overpotentials in Lithium Ion Conversion Reactions: Visualizing the Interface Evmenenko, Guennadi; Warburton, Robert E.; Yildirim, Handan ACS Nano, Vol. 13, Issue 7 https://doi.org/10.1021/acsnano.9b02007	journal	May 2019
Lithium Lanthanum Titanates: A Review Stramare, S.; Thangadurai, V.; Weppner, W. Chemistry of Materials, Vol. 15, Issue 21 https://doi.org/10.1021/cm0300516	journal	October 2003
Lithium Atom and A-Site Vacancy Distributions in Lanthanum Lithium Titanate Gao, Xiang; Fisher, Craig A. J.; Kimura, Teiichi Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm3041357	journal	April 2013
Interfacial Observation between LiCoO ₂ Electrode and Li ₂ S−P ₂ S ₅ Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy ^† Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm901819c	journal	February 2010
Li ₂ OHCl Crystalline Electrolyte for Stable Metallic Lithium Anodes Hood, Zachary D.; Wang, Hui; Samuthira Pandian, Amaresh Journal of the American Chemical Society, Vol. 138, Issue 6 https://doi.org/10.1021/jacs.5b11851	journal	January 2016
Real-Time Observations of Interfacial Lithiation in a Metal Silicide Thin Film Fister, Tim T.; Long, Brandon R.; Gewirth, Andrew A. The Journal of Physical Chemistry C, Vol. 116, Issue 42 https://doi.org/10.1021/jp305465j	journal	October 2012
Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach Lu, Jun; Zhan, Chun; Wu, Tianpin Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms6693	journal	December 2014
Understanding interface stability in solid-state batteries Xiao, Yihan; Wang, Yan; Bo, Shou-Hang Nature Reviews Materials, Vol. 5, Issue 2 https://doi.org/10.1038/s41578-019-0157-5	journal	December 2019
Designing solid-state electrolytes for safe, energy-dense batteries Zhao, Qing; Stalin, Sanjuna; Zhao, Chen-Zi Nature Reviews Materials, Vol. 5, Issue 3 https://doi.org/10.1038/s41578-019-0165-5	journal	February 2020
Domain boundary structures in lanthanum lithium titanates Gao, Xiang; Fisher, Craig A. J.; Kimura, Teiichi J. Mater. Chem. A, Vol. 2, Issue 3 https://doi.org/10.1039/c3ta13726k	journal	January 2014
Understanding the electronic and ionic conduction and lithium over-stoichiometry in LiMn ₂ O ₄ spinel Hoang, Khang J. Mater. Chem. A, Vol. 2, Issue 43 https://doi.org/10.1039/c4ta04116j	journal	January 2014
Electrode–electrolyte interfaces in lithium-based batteries Yu, Xingwen; Manthiram, Arumugam Energy & Environmental Science, Vol. 11, Issue 3 https://doi.org/10.1039/c7ee02555f	journal	January 2018
Structural analysis of the initial lithiation of NiO thin film electrodes Evmenenko, Guennadi; Fister, Timothy T.; Castro, Fernando C. Physical Chemistry Chemical Physics, Vol. 21, Issue 17 https://doi.org/10.1039/c9cp01527b	journal	January 2019
DFT modelling of explicit solid–solid interfaces in batteries: methods and challenges Leung, Kevin Physical Chemistry Chemical Physics, Vol. 22, Issue 19 https://doi.org/10.1039/c9cp06485k	journal	January 2020
The adsorption and oxidation of SO ₂ on MgO surface: experimental and DFT calculation studies Wang, Honghong; Zhong, Cheng; Ma, Qingxin Environmental Science: Nano, Vol. 7, Issue 4 https://doi.org/10.1039/c9en01474h	journal	January 2020
Universal Ti-rich termination of atomically flat SrTiO3 (001), (110), and (111) surfaces Biswas, A.; Rossen, P. B.; Yang, C. -H. Applied Physics Letters, Vol. 98, Issue 5 https://doi.org/10.1063/1.3549860	journal	January 2011
Flat-histogram method comparison on the two-dimensional Ising model Pommerenck, Jordan K.; Roundy, David Physical Review E, Vol. 102, Issue 3 https://doi.org/10.1103/PhysRevE.102.033306	journal	September 2020
First-principles calculation of the configurational energy density of states for a solid-state ion conductor with a variant of the Wang and Landau algorithm Howard, Jason D. Physical Review E, Vol. 102, Issue 6 https://doi.org/10.1103/PhysRevE.102.063304	journal	December 2020
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/physrev.136.b864	journal	November 1964
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/physrevb.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/physrevb.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/physrevb.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/physrevb.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/physrevb.59.1758	journal	January 1999
Surface structure and equilibrium particle shape of the LiMn 2 O 4 spinel from first-principles calculations Karim, Altaf; Fosse, Sonia; Persson, Kristin A. Physical Review B, Vol. 87, Issue 7 https://doi.org/10.1103/physrevb.87.075322	journal	February 2013
Structures, Li + mobilities, and interfacial properties of solid electrolytes Li 3 PS 4 and Li 3 PO 4 from first principles Lepley, N. D.; Holzwarth, N. A. W.; Du, Yaojun A. Physical Review B, Vol. 88, Issue 10 https://doi.org/10.1103/physrevb.88.104103	journal	September 2013
Modeling interfaces between solids: Application to Li battery materials Lepley, N. D.; Holzwarth, N. A. W. Physical Review B, Vol. 92, Issue 21 https://doi.org/10.1103/physrevb.92.214201	journal	December 2015
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/physrevlett.77.3865	journal	October 1996
Co-refinement of multiple-contrast neutron/X-ray reflectivity data using MOTOFIT Nelson, Andrew Journal of Applied Crystallography, Vol. 39, Issue 2 https://doi.org/10.1107/s0021889806005073	journal	March 2006
Review—Interfaces: Key Issue to Be Solved for All Solid-State Lithium Battery Technologies Ding, Zhanlai; Li, Jianlong; Li, Jiao Journal of The Electrochemical Society, Vol. 167, Issue 7 https://doi.org/10.1149/1945-7111/ab7f84	journal	March 2020
Recent Progresses in Nanometer Scale Analysis of Buried Layers and Interfaces in Thin Films by X-rays and Neutrons Stoev, Krassimir; Sakurai, Kenji Analytical Sciences, Vol. 36, Issue 8 https://doi.org/10.2116/analsci.19r010	journal	January 2020
Interfaces Between Cathode and Electrolyte in Solid State Lithium Batteries: Challenges and Perspectives Nie, Kaihui; Hong, Yanshuai; Qiu, Jiliang Frontiers in Chemistry, Vol. 6 https://doi.org/10.3389/fchem.2018.00616	journal	December 2018

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Title: Understanding the Solid-State Electrode–Electrolyte Interface of a Model System Using First-Principles Statistical Mechanics and Thin-Film X-ray Characterization

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