Characterization of two phase distribution in electrochemically-lithiated spinel Li4Ti5O12 secondary particles by electron energy-loss spectroscopy

Kitta, Mitsunori; Akita, Tomoki; Tanaka, Shingo; Kohyama, Masanori

doi:10.1016/j.jpowsour.2013.03.022

Cited by 60 publications

(61 citation statements)

References 40 publications

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“…It is well known that there is no obvious change in the XRD pattern during Li þ insertion/extraction in LTO, which is the 'zero-strain' characteristic of Li insertion. [30][31][32][33] The reason that no obvious new peaks were captured during the Mg 2 þ insertion/ extraction in the LTO might be attributed to the very closed ionic radii of the Mg ion (0.062 nm) and Li ion (0.068 nm). We believe that the excellent cycling stability of LTO in a Mg battery could benefit from the small volume changes during the charging-discharging process.…”

Section: Resultsmentioning

confidence: 99%

“…Thus, Mg 2 þ insertion is expected to be analogous to the insertion process of Li þ /Na þ . [30][31][32][33][34][35] At the beginning of the first Mg insertion process, Mg ions are more likely to occupy the 16c sites of the Li4 phase (where the Li 16d ions are nearly fixed) to form the Mg4Li phase. At the same time, the Li 8a ions, accompanying the other Li ions in the 8a sites of the nearest-neighbor Li4 phase, are pushed by Mg 2 þ to the 16c sites of the nearest-neighbor Li4 phase to form the new Li7 phase.…”

Section: Resultsmentioning

confidence: 99%

“…This mechanism is different from the classical Li þ /Na þ insertion/ extraction mechanism in LTO. [30][31][32][33][34][35] Furthermore, the most desirable property of this material is that after the initial activation the volume change during the Mg-ion insertion and extraction is only B0.8%, which shows the 'zero-strain' characteristics, thereby ensuring a long cycle life, as demonstrated by a good capacity retention of 495% after 500 cycles. Our finding is a new mechanism of Mg-ion storage in the LTO host lattice and offers an alternative Mg-ion insertion material for rechargeable Mg ion batteries.…”

Section: Introductionmentioning

confidence: 99%

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A highly reversible, low-strain Mg-ion insertion anode material for rechargeable Mg-ion batteries

et al. 2014

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Rechargeable magnesium (Mg) batteries have been attracting increasing attention recently because of the abundance of the raw material, their relatively low price and their good safety characteristics. However, rechargeable Mg batteries are still in their infancy. Therefore, alternate Mg-ion insertion anode materials are highly desirable to ultimately mass-produce rechargeable Mg batteries. In this study, we introduce the spinel Li 4 Ti 5 O 12 as an Mg-ion insertion-type anode material with a high reversible capacity of 175 mA h g À1 . This material possesses a low-strain characteristic, resulting in an excellent long-term cycle life. The proposed Mg-storage mechanism, including phase separation and transition reaction, is evaluated using advanced atomic scale scanning transmission electron microscopy techniques. This unusual Mg storage mechanism has rarely been reported for ion insertion-type electrode materials for rechargeable batteries. Our findings offer more options for the development of Mg-ion insertion materials for long-life rechargeable Mg batteries. NPG Asia Materials (2014) 6, e120; doi:10.1038/am.2014.61; published online 22 August 2014 INTRODUCTIONWith growing concern about the environment, climate change and a sustainable energy supply, studies have been focused on the development of green energy storage systems with high volumetric energy density, low price and improved safety. Compared to lithium battery systems, 1-6 rechargeable magnesium (Mg) batteries are considered to be a prospective candidate for reversible energy storage because of the great abundance of Mg resources, better chemical stability of metallic Mg in humid and oxygen-containing environments and higher volumetric capacity. [7][8][9] In particular, the increasing attention to rechargeable Mg batteries is due to the pioneering work of Aurbach's group. 10-14 Some progress has been achieved toward designing electrode materials 10,15-24 and electrolytes 25-29 for rechargeable Mg batteries. Nevertheless, rechargeable Mg batteries are still in their infancy. Therefore, alternative Mg-ion insertion anode materials are highly desirable to ultimately mass-produce rechargeable Mg-ion batteries. Recently, we have discovered the feasibility of utilizing spinel Li 4 Ti 5 O 12 , which is well known as a 'zero-strain' anode material for long-life stationary lithium-ion batteries, as an anode material for rechargeable Mg batteries. In this work, we further show that spinel Li 4 Ti 5 O 12 nanoparticles (LTO NPs) can exhibit excellent Mg storage performance under optimized conditions for rechargeable Mg batteries. This material shows a high reversible capacity of B175 mA h g À1 and superior cycling performance. By using an advanced atomic resolution scanning transmission electron

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A highly reversible, low-strain Mg-ion insertion anode material for rechargeable Mg-ion batteries

et al. 2014

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“…6 LTO presents a nearly constant potential plateau, which indicates that LTO undergoes a phase transformation. [14][15][16][17][18][19] Therefore, in the context of these LTO || NMC cells, the LTO electrode behaves in a way reminiscent of a reference electrode. As a result, the main visible features in the cell's IC curve originate from the PEAM.…”

Section: Resultsmentioning

confidence: 99%

“…[8][9][10][11][12][13] LTO, as a negative electrode active material (NEAM), presents some unique features such as zero strain in Li intercalation and a potential plateau (1.56 V vs. Li/Li + ) over the entire stoichiometry of intercalation with Li, which is relatively high compared to that of the carbonaceous NEAM typically used in commercial LIBs today. [14][15][16][17][18][19] This high potential plateau renders it stable against conventional LIB electrolytes, with minimal solid electrolyte interphase (SEI) presence to impede intercalation kinetics (i.e. allowing a better rate capability), but at the expense of energy density.…”

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confidence: 99%

Overcharge Study in Li₄Ti₅O₁₂Based Lithium-Ion Pouch Cell

Devie

Dubarry

Liaw

2015

J. Electrochem. Soc.

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Overcharge tolerance has often been studied from a safety standpoint (e.g. thermal runaway), but rarely from a durability standpoint. A quantitative battery diagnosis was developed to analyze an overcharge event in a commercial Li 4 Ti 5 O 12 || LiNi 1/3 Mn 1/3 Co 1/3 O 2 lithium-ion pouch cell and the subsequent cycle aging behavior. Using an electrochemical inference technique and the degradation emulation 'alawa toolbox, quantitative diagnoses of two cells enduring the same cycle aging conditions, with or without the overcharge event respectively, were performed. The baseline cell, which suffered from loss of active material in the positive electrode along with loss of lithium inventory in side-reactions, demonstrated excellent capacity retention (with 99.6% after 700 cycles). In contrast, the overcharged cell suffered from a larger capacity fade (15% immediately after the overcharge, and 23% after 700 cycles). We identified the loss of active material in the negative electrode as the culprit for capacity fade by the overcharge. Loss of active material in the positive electrode as well as loss of lithium inventory were also identified but did not contribute to the capacity fade. A hypothesis of localized blockage of the ionic conduction pathway due to gas accumulation was proposed as the mechanism driving the observed degradation.

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Toward Optimal Performance and In‐Depth Understanding of Spinel Li₄Ti₅O₁₂ Electrodes through Phase Field Modeling

Vasileiadis

Klerk

Smith

et al. 2018

Adv Funct Materials

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Computational modeling is vital for the fundamental understanding of processes in Li-ion batteries. However, capturing nanoscopic to mesoscopic phase thermodynamics and kinetics in the solid electrode particles embedded in realistic electrode morphologies is challenging. In particular for electrode materials displaying a first order phase transition, such as LiFePO 4 , graphite and spinel Li 4 Ti 5 O 12 , predicting the macroscopic electrochemical behavior requires an accurate physical model. Herein, we present a thermodynamic phase field model for Li-ion insertion in spinel Li 4 Ti 5 O 12 which captures the performance limitations presented in literature as a function of all relevant electrode parameters. The phase stability in the model is based on ab-initio DFT calculations and the Li-ion diffusion parameters on nanoscopic NMR measurements of Li-ion mobility, resulting in a parameter free model. The direct comparison with prepared electrodes shows good agreement over three orders of magnitude in the discharge current. Overpotentials associated with the various charge transport processes, as well as the active particle fraction relevant for local hotspots in batteries, are analyzed. It is demonstrated which process limits the electrode performance under a variety of realistic conditions, providing comprehensive understanding of the nanoscopic to microscopic properties. These results provide concrete directions towards the design of optimally performing Li 4 Ti 5 O 12 electrodes.

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Characterization of two phase distribution in electrochemically-lithiated spinel Li4Ti5O12 secondary particles by electron energy-loss spectroscopy

Cited by 60 publications

References 40 publications

A highly reversible, low-strain Mg-ion insertion anode material for rechargeable Mg-ion batteries

A highly reversible, low-strain Mg-ion insertion anode material for rechargeable Mg-ion batteries

Overcharge Study in Li₄Ti₅O₁₂Based Lithium-Ion Pouch Cell

Toward Optimal Performance and In‐Depth Understanding of Spinel Li₄Ti₅O₁₂ Electrodes through Phase Field Modeling

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Characterization of two phase distribution in electrochemically-lithiated spinel Li4Ti5O12 secondary particles by electron energy-loss spectroscopy

Cited by 60 publications

References 40 publications

A highly reversible, low-strain Mg-ion insertion anode material for rechargeable Mg-ion batteries

A highly reversible, low-strain Mg-ion insertion anode material for rechargeable Mg-ion batteries

Overcharge Study in Li4Ti5O12Based Lithium-Ion Pouch Cell

Toward Optimal Performance and In‐Depth Understanding of Spinel Li4Ti5O12 Electrodes through Phase Field Modeling

Contact Info

Product

Resources

About

Overcharge Study in Li₄Ti₅O₁₂Based Lithium-Ion Pouch Cell

Toward Optimal Performance and In‐Depth Understanding of Spinel Li₄Ti₅O₁₂ Electrodes through Phase Field Modeling