Lithium diffusion in the spinel phase<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext>Li</mml:mtext><mml:mn>4</mml:mn></mml:msub></mml:math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext>Ti</mml:mtext><mml:mn>5</mml:mn></mml:msub></mml:math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext>O</mml:mtext><mml:mn>12</mml:mn></mml:msub></mml:math>and in the rocksalt phase<mml:math xmlns:mml="http://www.w3.org/1998/Math/Math

Ziebarth, Benedikt; Klinsmann, Markus; Eckl, Thomas; Elsässer, Christian

doi:10.1103/physrevb.89.174301

Cited by 112 publications

(74 citation statements)

References 18 publications

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“…The lower one is set as reference.to find out the most favorable arrangement of Li and Ti atoms at the 16d sites to obtain a reasonable bulk model. In the most stable configuration, the two Li 16d atoms have the largest distances and a layer at c/2 of the supercell is occupied by Li atoms only, that shows a similar atom arrangement in other reported structures 42,43. Figure 2…”

mentioning

confidence: 65%

Tailoring Native Defects and Zinc Impurities in Li₄Ti₅O₁₂: Insights from First-Principles Study

Duan

et al. 2015

J. Phys. Chem. C

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We report first-principles density functional theory (DFT) studies of native defects and zinc impurities in Li 4 Ti 5 O 12 , as a promising anode material for rechargeable Li-ion batteries. The defects are characterized by their formation energies, electronic properties and geometrical structures. The Ti vacancy and the Li antisite as multiple acceptor defects in p-type samples are preferred under O-rich conditions, while the Ti interstitial and Ti antisite are energetically favorable under O-poor conditions. In Zn-doped LTO, substitutional Zn located at the 8a Li site is preferable to form under reducing condition, which brings a feasible decrease in TiO 6 octahedral distortion and has a potential effect on the Li ion diffusion. For all native defects and Zn impurities, no localized states are found in the calculated band gap and their formation energies are all sensitive to the atomic chemical potentials and Fermi energy, which provide insights on how to design a rational defect-controlled synthesis condition to enhance the LTO's electrochemical performance for targeted applications.

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confidence: 65%

Tailoring Native Defects and Zinc Impurities in Li₄Ti₅O₁₂: Insights from First-Principles Study

Duan

et al. 2015

J. Phys. Chem. C

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“…Some potential reasons for symmetry breaking in our system are: (i) the manufacturing process leads to a Pt bottom electrode that has been exposed to higher temperatures, while the Pt top electrode is deposited at room temperature; (ii) in similar spinel systems it has been shown that a Li‐rich nanometric layer is generated during film preparation, which can cause a thermodynamically favorable state where one of the phases wet the Pt electrode. (iii) the 16d positions are randomly populated by Ti and Li ions with a ratio 5:1, and this is known to affect Li‐ion pathways in the bulk . The latter is further supported by Atomic Force Microscopy measurements, in which topography and phase maps show clear contrast between grains, Figure S7.…”

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confidence: 68%

“…As noted above, this subtle difference in the permittivity can explain the different hysteretic behavior between the measured current‐voltage curves, Figure a‐b, for Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 , respectively. The difference in retention can be explained in terms of Li‐diffusivity of the phase‐separated filament, e.g., the Li 7 Ti 5 O 12 filaments created in the Li 4 Ti 5 O 12 device would tend to lower retention values, given the higher diffusivity of Li‐ions in the Li 7 Ti 5 O 12 phase . However, at this stage, the size and composition of the filaments remains as an open question, which should be unveiled by advanced characterization techniques.…”

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confidence: 99%

Lithium‐Battery Anode Gains Additional Functionality for Neuromorphic Computing through Metal–Insulator Phase Separation

et al. 2020

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Specialized hardware for neural networks requires materials with tunable symmetry, retention, and speed at low power consumption. The study proposes lithium titanates, originally developed as Li‐ion battery anode materials, as promising candidates for memristive‐based neuromorphic computing hardware. By using ex‐ and in operando spectroscopy to monitor the lithium filling and emptying of structural positions during electrochemical measurements, the study also investigates the controlled formation of a metallic phase (Li7Ti5O12) percolating through an insulating medium (Li4Ti5O12) with no volume changes under voltage bias, thereby controlling the spatially averaged conductivity of the film device. A theoretical model to explain the observed hysteretic switching behavior based on electrochemical nonequilibrium thermodynamics is presented, in which the metal‐insulator transition results from electrically driven phase separation of Li4Ti5O12 and Li7Ti5O12. Ability of highly lithiated phase of Li7Ti5O12 for Deep Neural Network applications is reported, given the large retentions and symmetry, and opportunity for the low lithiated phase of Li4Ti5O12 toward Spiking Neural Network applications, due to the shorter retention and large resistance changes. The findings pave the way for lithium oxides to enable thin‐film memristive devices with adjustable symmetry and retention.

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“…At the interface between the LTO and liquid electrolyte at 1.5 V vs. Li/Li + , there is no electrolyte reduction reaction and therefore no SEI is formed on LTO at 1. 29 With no SEI and fast Li + conduction in LTO, the Li + de-solvation process is a rate limiting step at the LTO and electrolyte interface.…”

Section: Discussionmentioning

confidence: 99%

Factors Limiting Li⁺Charge Transfer Kinetics in Li-Ion Batteries

Jow

Delp

Allen

et al. 2018

J. Electrochem. Soc.

301

190

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Understanding the factors limiting Li + charge transfer kinetics in Li-ion batteries is essential in improving the rate performance, especially at lower temperatures. The Li + charge transfer process involved in the lithium intercalation of graphite anode includes the step of de-solvation of the solvated Li + in the liquid electrolyte and the step of transport of Li + in the preformed solid electrolyte interphase (SEI) on electrodes until the Li + accepts an electron at the electrode and becomes a Li in the electrode. Whether the de-solvation process or the Li + transport through the SEI is a limiting step depends on the nature of the interphases at the electrode and electrolyte interfaces. Several examples involving the electrode materials such as graphite, lithium titanate (LTO), lithium iron phosphate (LFP), lithium nickel cobalt aluminum oxide (NCA) and solid Li + conductor such as lithium lanthanum titanate or Li-Al-Ti-phosphate are reviewed and discussed to clarify the conditions at which either the de-solvation or the transport of Li + in SEI is dominating and how the electrolyte components affect the activation energy of Li + charge transfer kinetics. How the electrolyte additives impact the Li + charge transfer kinetics at both the anode and the cathode has been examined at the same time in 3-electrode full cells. The resulting impact on Li + charge transfer resistance, R ct , and activation energy, E a , at both electrodes are reported and discussed. To improve the power performance of Li-ion batteries, it is important to understand the factors that limit the Li + charge transfer kinetics. Li-ion batteries comprised of a graphite anode and a lithium cobalt oxide cathode in an electrolyte consisting of 1 M LiPF 6 in ethylene carbonate (EC)-dimethyl carbonate (DMC)-diethyl carbonate (DEC) carbonate solvent mixture could not deliver their room temperature capacity at a rate of C/2 at −30 and −40• C. 1 When DEC was replaced by a linear ester solvent, such as ethyl acetate (EA) or methyl butyrate (MB), the Li-ion batteries at −30 and −40• C could deliver over 80% of their room temperature capacity at the same rate.2 When the LiPF 6 salt is replaced by lithium bis(oxalato)borate (LiBOB) in EC-ethyl methyl carbonate (EMC) (1:1 wt ratio) carbonate solvent mixture, the impedance of the graphite-electrolyte interface measured using graphite/Li half cells in the electrolyte with LiBOB is three times that in the electrolyte with LiPF 6 .3 These examples illustrate that the electrolyte components play crucial roles in affecting Li + charge transfer kinetics in Li-ion batteries.The Li + charge transfer process starts from the solvated Li + in the electrolyte to the reception of an electron (e − ) from the electrode and becomes Li (i.e., Li x C in graphitic anodes). This involves the desolvation step of Li + before entering into a layer of solid electrolyte interphases, or SEI, that is often referred to that on the anode such as carbonaceous materials, and the diffusion step of Li + through the SEI, which is pre-form...

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Lithium diffusion in the spinel phaseLi4Ti5O12and in the rocksalt phase
Benedikt Ziebarth
¹
,
Markus Klinsmann
²
,
Thomas Eckl
³

et al.

Cited by 112 publications

References 18 publications

Tailoring Native Defects and Zinc Impurities in Li₄Ti₅O₁₂: Insights from First-Principles Study

Tailoring Native Defects and Zinc Impurities in Li₄Ti₅O₁₂: Insights from First-Principles Study

Lithium‐Battery Anode Gains Additional Functionality for Neuromorphic Computing through Metal–Insulator Phase Separation

Factors Limiting Li⁺Charge Transfer Kinetics in Li-Ion Batteries

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Lithium diffusion in the spinel phaseLi4Ti5O12and in the rocksalt phaseBenedikt Ziebarth1, Markus Klinsmann2, Thomas Eckl3 et al.

Cited by 112 publications

References 18 publications

Tailoring Native Defects and Zinc Impurities in Li4Ti5O12: Insights from First-Principles Study

Tailoring Native Defects and Zinc Impurities in Li4Ti5O12: Insights from First-Principles Study

Lithium‐Battery Anode Gains Additional Functionality for Neuromorphic Computing through Metal–Insulator Phase Separation

Factors Limiting Li+Charge Transfer Kinetics in Li-Ion Batteries

Contact Info

Product

Resources

About

Lithium diffusion in the spinel phaseLi4Ti5O12and in the rocksalt phase
Benedikt Ziebarth
¹
,
Markus Klinsmann
²
,
Thomas Eckl
³

et al.

Tailoring Native Defects and Zinc Impurities in Li₄Ti₅O₁₂: Insights from First-Principles Study

Tailoring Native Defects and Zinc Impurities in Li₄Ti₅O₁₂: Insights from First-Principles Study

Factors Limiting Li⁺Charge Transfer Kinetics in Li-Ion Batteries