Imaging phase boundary kinetics in lithium titanate using operando electron energy-loss spectroscopy

Yuki Nomura; Kazuo Yamamoto; Naoaki Kuwata; Tsukasa Hirayama

doi:10.51094/jxiv.3245

##article.authors##

Yuki Nomura Nanostructures Research Laboratory, Japan Fine Ceramics Center https://orcid.org/0000-0002-6091-5902 https://researchmap.jp/nomurayuki
Kazuo Yamamoto Nanostructures Research Laboratory, Japan Fine Ceramics Center
Naoaki Kuwata Research Center for Energy and Environmental Materials, National Institute for Materials Science
Tsukasa Hirayama Nanostructures Research Laboratory, Japan Fine Ceramics Center

DOI:

https://doi.org/10.51094/jxiv.3245

キーワード:

Activation energy、 Diffusion、 Extraction、 Kinetic Parameters、 Phase Transitions

抄録

Lithium titanate accommodates and releases lithium ions through phase separation. The dynamics of the phase boundary movement are critical to battery performance, particularly for maximizing the charge/discharge rates. However, details of this boundary movement remain unclear. Here, we visualize the phase boundary movement by tracking the Li distribution using operando scanning transmission electron microscopy coupled with electron energy-loss spectroscopy. For Li insertion, the rate constants of the phase boundary movement were 3.6 ± 0.9 × 10⁻¹³ cm²/s at 30 °C and 3.2 ± 0.3 × 10⁻¹¹ cm²/s at 105 °C, whereas for Li extraction they were 4.0 ± 0.7 × 10⁻¹¹ cm²/s at 30 °C and 1.9 ± 0.6 × 10⁻⁹ cm²/s at 105 °C. The activation energies for Li-ion diffusion were 0.49 and 0.59 eV for Li₄Ti₅O₁₂ and Li₇Ti₅O₁₂, respectively. The relatively low activation energy of 0.49 eV is the reason why lithium titanate exhibits high-rate discharge performance.

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The authors declare no competing financial interest.

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引用文献

(1) Ohzuku, T.; Ueda, A.; Yamamoto, N. Zero-Strain Insertion Material of Li[Li1/3Ti5/3]O4 for Rechargeable Lithium Cells. J. Electrochem. Soc. 1995, 142 (5), 1431–1435.

(2) Takami, N.; Hoshina, K.; Inagaki, H. Lithium Diffusion in Li4/3Ti5/3O4 Particles during Insertion and Extraction. J. Electrochem. Soc. 2011, 158 (6), A725–A730.

(3) Zhu, G.-N.; Wang, Y.-G.; Xia, Y.-Y. Ti-Based Compounds as Anode Materials for Li-Ion Batteries. Energy Environ. Sci. 2012, 5 (5), 6652–6667.

(4) Yi, T.-F.; Yang, S.-Y.; Xie, Y. Recent Advances of Li4Ti5O12 as a Promising next Generation Anode Material for High Power Lithium-Ion Batteries. J. Mater. Chem. A 2015, 3 (11), 5750–5777.

(5) Yuan, T.; Tan, Z.; Ma, C.; Yang, J.; Ma, Z.-F.; Zheng, S. Challenges of Spinel Li4Ti5O12 for Lithium-Ion Battery Industrial Applications. Adv. Energy Mater. 2017, 7 (12), 1601625.

(6) Zhang, H.; Yang, Y.; Xu, H.; Wang, L.; Lu, X.; He, X. Li4Ti5O12 Spinel Anode: Fundamentals and Advances in Rechargeable Batteries. InfoMat 2022, 4 (4), e12228.

(7) Ding, X.; Zhou, Q.; Li, X.; Xiong, X. Fast-Charging Anodes for Lithium Ion Batteries: Progress and Challenges. Chem. Commun. 2024, 60 (18), 2472–2488.

(8) Koerver, R.; Aygün, I.; Leichtweiß, T.; Dietrich, C.; Zhang, W.; Binder, J. O.; Hartmann, P.; Zeier, W. G.; Janek, J. Capacity Fade in Solid-State Batteries: Interphase Formation and Chemomechanical Processes in Nickel-Rich Layered Oxide Cathodes and Lithium Thiophosphate Solid Electrolytes. Chem. Mater. 2017, 29 (13), 5574–5582.

(9) Xiao, Y.; Wang, Y.; Bo, S.-H.; Kim, J. C.; Miara, L. J.; Ceder, G. Understanding Interface Stability in Solid-State Batteries. Nat. Rev. Mater. 2020, 5, 105–126.

(10) Wu, X.; Villevieille, C.; Novák, P.; El Kazzi, M. Insights into the Chemical and Electronic Interface Evolution of Li4Ti5O12 Cycled in Li2S–P2S5 Enabled by Operando X-Ray Photoelectron Spectroscopy. J. Mater. Chem. A 2020, 8 (10), 5138–5146.

(11) Banerjee, A.; Wang, X.; Fang, C.; Wu, E. A.; Meng, Y. S. Interfaces and Interphases in All-Solid-State Batteries with Inorganic Solid Electrolytes. Chem. Rev. 2020, 120 (14), 6878–6933.

(12) Nomura, Y.; Yamamoto, K. Advanced Characterization Techniques for Sulfide-Based Solid-State Lithium Batteries. Adv. Energy Mater. 2023, 13 (13), 2203883.

(13) Kitta, M.; Akita, T.; Tanaka, S.; Kohyama, M. Two-Phase Separation in a Lithiated Spinel Li4Ti5O12 Crystal as Confirmed by Electron Energy-Loss Spectroscopy. J. Power Sources 2014, 257, 120–125.

(14) Matsuda, Y.; Kuwata, N.; Kawamura, J. Thin-Film Lithium Batteries with 0.3–30 Μm Thick LiCoO2 Films Fabricated by High-Rate Pulsed Laser Deposition. Solid State Ionics 2018, 320, 38–44.

(15) Joshi, Y.; Lawitzki, R.; Schmitz, G. Slow-Moving Phase Boundary in Li4/3+xTi5/3O4. Small Methods 2021, 5 (10), 2100532.

(16) Wagemaker, M.; Simon, D. R.; Kelder, E. M.; Schoonman, J.; Ringpfeil, C.; Haake, U.; Lützenkirchen-Hecht, D.; Frahm, R.; Mulder, F. M. A Kinetic Two-Phase and Equilibrium Solid Solution in Spinel Li4+xTi5O12. Adv. Mater. 2006, 18 (23), 3169–3173.

(17) Wagemaker, M.; van Eck, E. R. H.; Kentgens, A. P. M.; Mulder, F. M. Li-Ion Diffusion in the Equilibrium Nanomorphology of Spinel Li4+xTi5O12. J. Phys. Chem. B 2009, 113 (1), 224–230.

(18) Schmidt, W.; Bottke, P.; Sternad, M.; Gollob, P.; Hennige, V.; Wilkening, M. Small Change—Great Effect: Steep Increase of Li Ion Dynamics in Li4Ti5O12 at the Early Stages of Chemical Li Insertion. Chem. Mater. 2015, 27 (5), 1740–1750.

(19) Schmidt, W.; Wilkening, M. Discriminating the Mobile Ions from the Immobile Ones in Li4+xTi5O12: 6Li NMR Reveals the Main Li+ Diffusion Pathway and Proposes a Refined Lithiation Mechanism. J. Phys. Chem. C 2016, 120 (21), 11372–11381.

(20) Ganapathy, S.; Vasileiadis, A.; Heringa, J. R.; Wagemaker, M. The Fine Line between a Two-Phase and Solid-Solution Phase Transformation and Highly Mobile Phase Interfaces in Spinel Li4+xTi5O12. Adv. Energy Mater. 2017, 7 (9), 1601781.

(21) Zhang, W.; Seo, D.-H.; Chen, T.; Wu, L.; Topsakal, M.; Zhu, Y.; Lu, D.; Ceder, G.; Wang, F. Kinetic Pathways of Ionic Transport in Fast-Charging Lithium Titanate. Science 2020, 367 (6481), 1030–1034.

(22) Pyun, S.-I.; Ryu, Y.-G. Lithium Transport through Graphite Electrodes That Contain Two Stage Phases. J. Power Sources 1998, 70 (1), 34–39.

(23) Funabiki, A.; Inaba, M.; Abe, T.; Ogumi, Z. Stage Transformation of Lithium-Graphite Intercalation Compounds Caused by Electrochemical Lithium Intercalation. J. Electrochem. Soc. 1999, 146 (7), 2443–2448.

(24) Funabiki, A.; Inaba, M.; Abe, T.; Ogumi, Z. Nucleation and Phase-Boundary Movement upon Stage Transformation in Lithium–Graphite Intercalation Compounds. Electrochim. Acta 1999, 45 (6), 865–871.

(25) Levi, M. D.; Markevich, E.; Aurbach, D. The Effect of Slow Interfacial Kinetics on the Chronoamperometric Response of Composite Lithiated Graphite Electrodes and on the Calculation of the Chemical Diffusion Coefficient of Li Ions in Graphite. J. Phys. Chem. B 2005, 109 (15), 7420–7427.

(26) Levi, M. D.; Markevich, E.; Aurbach, D. Comparison between Cottrell Diffusion and Moving Boundary Models for Determination of the Chemical Diffusion Coefficients in Ion-Insertion Electrodes. Electrochim. Acta 2005, 51 (1), 98–110.

(27) Wilkening, M.; Amade, R.; Iwaniak, W.; Heitjans, P. Ultraslow Li Diffusion in Spinel-Type Structured Li4Ti5O12—a Comparison of Results from Solid State NMR and Impedance Spectroscopy. Phys. Chem. Chem. Phys. 2007, 9 (10), 1239–1246.

(28) Dees, D. W.; Kawauchi, S.; Abraham, D. P.; Prakash, J. Analysis of the Galvanostatic Intermittent Titration Technique (GITT) as Applied to a Lithium-Ion Porous Electrode. J. Power Sources 2009, 189 (1), 263–268.

(29) Zhu, Y.; Wang, C. Galvanostatic Intermittent Titration Technique for Phase-Transformation Electrodes. J. Phys. Chem. C 2010, 114 (6), 2830–2841.

(30) Oyama, G.; Yamada, Y.; Natsui, R.-I.; Nishimura, S.-I.; Yamada, A. Kinetics of Nucleation and Growth in Two-Phase Electrochemical Reaction of LixFePO4. J. Phys. Chem. C 2012, 116 (13), 7306–7311.

(31) Crain, D. J.; Zheng, J. P.; Roy, D. Electrochemical Examination of Core–Shell Mediated Li+ Transport in Li4Ti5O12 Anodes of Lithium Ion Batteries. Solid State Ionics 2013, 240 (1), 10–18.

(32) Kuwata, N.; Nakane, M.; Miyazaki, T.; Mitsuishi, K.; Kawamura, J. Lithium Diffusion Coefficient in LiMn2O4 Thin Films Measured by Secondary Ion Mass Spectrometry with Ion-Exchange Method. Solid State Ionics 2018, 320, 266–271.

(33) Kuwata, N.; Hasegawa, G.; Maeda, D.; Ishigaki, N.; Miyazaki, T.; Kawamura, J. Tracer Diffusion Coefficients of Li Ions in LixMn2O4 Thin Films Observed by Isotope Exchange Secondary Ion Mass Spectrometry. J. Phys. Chem. C 2020, 124 (42), 22981–22992.

(34) Hasegawa, G.; Kuwata, N.; Ohnishi, T.; Takada, K. Visualization and Evaluation of Lithium Diffusion at Grain Boundaries in Li0.29La0.57TiO3 Solid Electrolytes Using Secondary Ion Mass Spectrometry. J. Mater. Chem. A 2024, 12 (2), 731–738.

(35) Yamamoto, K.; Iriyama, Y.; Asaka, T.; Hirayama, T.; Fujita, H.; Fisher, C. A. J.; Nonaka, K.; Sugita, Y.; Ogumi, Z. Dynamic Visualization of the Electric Potential in an All-Solid-State Rechargeable Lithium Battery. Angew. Chem. Int. Ed. 2010, 49 (26), 4414–4417.

(36) Huang, J. Y.; Zhong, L.; Wang, C. M.; Sullivan, J. P.; Xu, W.; Zhang, L. Q.; Mao, S. X.; Hudak, N. S.; Liu, X. H.; Subramanian, A.; Fan, H.; Qi, L.; Kushima, A.; Li, J. In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode. Science 2010, 330 (6010), 1515–1520.

(37) Yuan, Y.; Amine, K.; Lu, J.; Shahbazian-Yassar, R. Understanding Materials Challenges for Rechargeable Ion Batteries with in Situ Transmission Electron Microscopy. Nat. Commun. 2017, 8, 15806.

(38) Shang, T.; Wen, Y.; Xiao, D.; Gu, L.; Hu, Y.-S.; Li, H. Atomic-Scale Monitoring of Electrode Materials in Lithium-Ion Batteries Using in Situ Transmission Electron Microscopy. Adv. Energy Mater. 2017, 7 (23), 1700709.

(39) Masuda, H.; Matsushita, K.; Ito, D.; Fujita, D.; Ishida, N. Dynamically Visualizing Battery Reactions by Operando Kelvin Probe Force Microscopy. Commun. Chem. 2019, 2, 140.

(40) Wang, L.; Xie, R.; Chen, B.; Yu, X.; Ma, J.; Li, C.; Hu, Z.; Sun, X.; Xu, C.; Dong, S.; Chan, T.-S.; Luo, J.; Cui, G.; Chen, L. In-Situ Visualization of the Space-Charge-Layer Effect on Interfacial Lithium-Ion Transport in All-Solid-State Batteries. Nat. Commun. 2020, 11, 5889.

(41) Wan, J.; Yan, H.-J.; Wen, R.; Wan, L.-J. In Situ Visualization of Electrochemical Processes in Solid-State Lithium Batteries. ACS Energy Lett. 2022, 7 (9), 2988–3002.

(42) Wang, Z.; Santhanagopalan, D.; Zhang, W.; Wang, F.; Xin, H. L.; He, K.; Li, J.; Dudney, N.; Meng, Y. S. In Situ STEM-EELS Observation of Nanoscale Interfacial Phenomena in All-Solid-State Batteries. Nano Lett. 2016, 16 (6), 3760–3767.

(43) Nomura, Y.; Yamamoto, K.; Hirayama, T.; Igaki, E.; Saitoh, K. Visualization of Lithium Transfer Resistance in Secondary Particle Cathodes of Bulk-Type Solid-State Batteries. ACS Energy Lett. 2020, 5 (6), 2098–2105.

(44) Nomura, Y.; Yamamoto, K.; Yamagishi, Y.; Igaki, E. Lithium Transport Pathways Guided by Grain Architectures in Ni-Rich Layered Cathodes. ACS Nano 2021, 15 (12), 19806–19814.

(45) Nomura, Y.; Yamamoto, K.; Hirayama, T. Visualizing Asymmetric Phase Separation Driven by Surface Ionic Diffusion in Lithium Titanate. J. Mater. Chem. A 2023, 11 (43), 23243–23248.

(46) Tojo, T.; Kawashiri, S.; Tsuda, T.; Kadowaki, M.; Inada, R.; Sakurai, Y. Electrochemical Performance of Single Li4Ti5O12 Particle for Lithium Ion Battery Anode. J. Electroanal. Chem. 2019, 836 (1), 24–29.

(47) Rauch, E. F.; Portillo, J.; Nicolopoulos, S.; Bultreys, D.; Rouvimov, S.; Moeck, P. Automated Nanocrystal Orientation and Phase Mapping in the Transmission Electron Microscope on the Basis of Precession Electron Diffraction. Zeitschrift für Kristallographie 2010, 225, 103–109.

(48) Brunetti, G.; Robert, D.; Bayle-Guillemaud, P.; Rouvière, J. L.; Rauch, E. F.; Martin, J. F.; Colin, J. F.; Bertin, F.; Cayron, C. Confirmation of the Domino-Cascade Model by LiFePO4/FePO4 Precession Electron Diffraction. Chem. Mater. 2011, 23 (20), 4515–4524.

(49) Kitta, M.; Akita, T.; Tanaka, S.; Kohyama, M. Characterization of Two Phase Distribution in Electrochemically-Lithiated Spinel Li4Ti5O12 Secondary Particles by Electron Energy-Loss Spectroscopy. J. Power Sources 2013, 237, 26–32.

(50) Park, H.; Mesnier, A.; Lee, S.; Jarvis, K.; Manthiram, A.; Warner, J. H. Intrinsic Li Distribution in Layered Transition-Metal Oxides Using Low-Dose Scanning Transmission Electron Microscopy and Spectroscopy. Chem. Mater. 2021, 33 (12), 4638–4650.

(51) Fraggedakis, D.; Nadkarni, N.; Gao, T.; Zhou, T.; Zhang, Y.; Han, Y.; Stephens, R. M.; Shao-Horn, Y.; Bazant, M. Z. A Scaling Law to Determine Phase Morphologies during Ion Intercalation. Energy Environ. Sci. 2020, 13 (7), 2142–2152.

(52) Jost, W. Diffusion in Solids, Liquids, Gases; Academic Press, 1952.

(53) Douglass, D. L.; Wagner, C. The Oxidation of Oxygen-Deficient Zirconia and Its Relationship to the Oxidation of Zirconium. J. Electrochem. Soc. 1966, 113 (7), 671–676.

(54) Hain, H.; Scheuermann, M.; Heinzmann, R.; Wünsche, L.; Hahn, H.; Indris, S. Study of Local Structure and Li Dynamics in Li4+xTi5O12 (0 ≤ x ≤ 5) Using 6Li and 7Li NMR Spectroscopy. Solid State Nucl. Magn. Reson. 2012, 42, 9–16.

(55) Ziebarth, B.; Klinsmann, M.; Eckl, T.; Elsässer, C. Lithium Diffusion in the Spinel Phase Li4Ti5O12 and in the Rocksalt Phase Li7Ti5O12 of Lithium Titanate from First Principles. Phys. Rev. B 2014, 89, 174301.

(56) Takahashi, M.; Tobishima, S.-I.; Takei, K.; Sakurai, Y. Reaction Behavior of LiFePO4 as a Cathode Material for Rechargeable Lithium Batteries. Solid State Ionics 2002, 148 (3–4), 283–289.

(57) Iriyama, Y.; Kurita, H.; Yamada, I.; Abe, T.; Ogumi, Z. Effects of Surface Modification by MgO on Interfacial Reactions of Lithium Cobalt Oxide Thin Film Electrode. J. Power Sources 2004, 137 (1), 111–116.

(58) Doi, T.; Iriyama, Y.; Abe, T.; Ogumi, Z. Pulse Voltammetric and Ac Impedance Spectroscopic Studies on Lithium Ion Transfer at an Electrolyte/Li4/3Ti5/3O4 Electrode Interface. Anal. Chem. 2005, 77 (6), 1696–1700.

(59) Iriyama, Y.; Kako, T.; Yada, C.; Abe, T.; Ogumi, Z. Charge Transfer Reaction at the Lithium Phosphorus Oxynitride Glass Electrolyte/Lithium Cobalt Oxide Thin Film Interface. Solid State Ionics 2005, 176 (31–34), 2371–2376.