Nanostructured lithium titanate and lithium titanate/carbon nanocomposite as anode materials for advanced lithium-ion batteries

Xia, Hui; Luo, Zhentao; Xie, Jianping

doi:10.1515/ntrev-2012-0049

Cited by 20 publications

(9 citation statements)

References 105 publications

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“…Anode materials with lithium insertion potentials >0.28 V vs Li/Li + , such as lithium titanate, − have been successfully used with an aluminum current collector as a lithium-ion cell anode. However, the high extraction potential of lithium titanate, 1.4–1.6 V vs Li/Li + , and its low practical capacity of 120–180 mAh/g − compared to that of graphite (330–350 mAh/g) lead to a substantial decrease in the achievable lithium-ion cell specific energy and energy density. Other materials such as tin , have a significant portion of their alloying reaction with lithium occurring at potentials >0.3 V vs Li/Li + .…”

Section: Introductionmentioning

confidence: 99%

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Crompton¹,

Hladky²

2021

ACS Appl. Energy Mater.

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Reduction reactions with lithium at >0.3 V vs Li/Li + make germanium prospectively compatible with aluminum current collectors to form a copper-free lithium-ion cell anode that may enable lithium-ion cells that are more tolerant to overdischarge. Targeted 2.0 mAh/cm 2 germanium nanoparticle electrodes with an aluminum foil (Ge−Al electrode) current collector were fabricated and tested versus lithium from 0.3 to 1.5 V vs Li/Li + in 1.0 M LiPF 6 1:1 ethylene carbonate/diethyl carbonate (v/v) electrolyte and demonstrated a peak reversible capacity of 342 mAh/g Ge at a targeted C/10 rate. A targeted 2.0 mAh/cm 2 germanium nanoparticle electrode with a copper current collector (Ge−Cu electrode) was also tested from 0.005 to 1.5 V vs Li/Li + , the results of which are utilized as a representative comparison of germanium tested in a conventional lithium-ion anode potential range. Compared to the Ge−Cu electrode, after 50 cycles at a targeted C/10 rate the Ge−Al electrode showed 90% vs 18% capacity retention. Post-mortem analysis with XPS, SEM/EDS, Raman spectroscopy, and FTIR showed that compared to the Ge−Cu electrode the Ge−Al electrode had (1) less oxygen, fluorine, and carbon deposition, (2) less germanium amorphization, (3) formation of Li x C y and Ge−H, and (4) less Li 2 O formation. After 150 cycles at equivalent targeted rates, the Ge−Al electrode also had significantly less mid-frequency impedance growth than the Ge−Cu electrode. Modeling of 18650 format LiNiCoAlO 2 -cathode lithium-ion cells with a Ge−Al anode predicted an achievable energy density and specific energy of up to 491 Wh/L and 198 Wh/kg. A germanium dissolution potential of 4.2 V vs Li/Li + was assigned based on voltammetry and post-mortem SEM/EDS. Cycling of a Ge−Al electrode with an upper potential cutoff of 4.2 V vs Li/Li + every tenth cycle showed 30% capacity retention after 50 cycles, an increased capacity fade attributed to solid electrolyte interphase instability up to 4.2 V vs Li/Li + based on impedance and post-mortem analysis.

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Section: Introductionmentioning

confidence: 99%

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Crompton¹,

Hladky²

2021

ACS Appl. Energy Mater.

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“…Third, the novel hierarchical “flower-like” LTO microspheres, generated by our group recently, consist of thin “sawtooth”-shaped constituent nanosheets, providing for not only shortened Li-ion diffusion distances but also enhanced contact area with electrolyte. In effect, the overall micrometer-scale spherical assemblies themselves should give rise to not only outstanding thermodynamic stability but also high tap density. , …”

Section: Introductionmentioning

confidence: 99%

Structural and Electrochemical Characteristics of Ca-Doped “Flower-like” Li₄Ti₅O₁₂Motifs as High-Rate Anode Materials for Lithium-Ion Batteries

et al. 2018

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Doped motifs offer an intriguing structural pathway toward improving conductivity for battery applications. Specifically, Ca-doped, three-dimensional "flower-like" Li 4−x Ca x Ti 5 O 12 ("x" = 0, 0.1, 0.15, and 0.2) micrometer-scale spheres have been successfully prepared for the first time using a simple and reproducible hydrothermal reaction followed by a short calcination process. The products were experimentally characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) mapping, inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge−discharge testing. Calcium dopant ions were shown to be uniformly distributed within the LTO structure without altering the underlying "flower-like" morphology. The largest lattice expansion and the highest Ti 3+ ratios were noted with XRD and XPS, respectively, whereas increased charge transfer conductivity and decreased Li + -ion diffusion coefficients were displayed in EIS for the Li 4−x Ca x Ti 5 O 12 ("x" = 0.2) sample. The "x" = 0.2 sample yielded a higher rate capability, an excellent reversibility, and a superior cycling stability, delivering 151 and 143 mAh/g under discharge rates of 20C and 40C at cycles 60 and 70, respectively. In addition, a high cycling stability was demonstrated with a capacity retention of 92% after 300 cycles at a very high discharge rate of 20C. In addition, first-principles calculations based on density functional theory (DFT) were conducted with the goal of further elucidating and understanding the nature of the doping mechanism in this study. The DFT calculations not only determined the structure of the Ca-doped Li 4 Ti 5 O 12 , which was found to be in accordance with the experimentally measured XPD pattern, but also yielded valuable insights into the doping-induced effect on both the atomic and electronic structures of Li 4 Ti 5 O 12 .

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“…However, a few major drawbacks remain with the conventional synthetic methods. First, it is very difficult to synthesize nanoscale LTO particles with a small diameter of around 10 nm, where the particle size could possibly effectively improve the rate performance . Only a few methods have been developed to synthesize small LTO particles.…”

Section: Introductionmentioning

confidence: 99%

Scalable in Situ Synthesis of Li₄Ti₅O₁₂/Carbon Nanohybrid with Supersmall Li₄Ti₅O₁₂Nanoparticles Homogeneously Embedded in Carbon Matrix

Zheng

Wang

Xia

et al. 2018

ACS Appl. Mater. Interfaces

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LiTiO (LTO) is regarded as a promising lithium-ion battery anode due to its stable cyclic performance and reliable operation safety. The moderate rate performance originated from the poor intrinsic electron and lithium-ion conductivities of the LTO has significantly limited its wide applications. A facile scalable synthesis of hierarchical LiTiO/C nanohybrids with supersmall LTO nanoparticles (ca. 17 nm in diameter) homogeneously embedded in the continuous submicrometer-sized carbon matrix is developed. Difunctional methacrylate monomers are used as solvent and carbon source to generate TiO/C nanohybrid, which is in situ converted to LTO/C via a solid-state reaction procedure. The structure, morphology, crystallinity, composition, tap density, and electrochemical performance of the LTO/C nanohybrid are systematically investigated. Comparing to the control sample of the commercial LTO composited with carbon, the reversible specific capacity after 1000 cycles at 175 mA g and rate performance at high current densities (875, 1750, and 3500 mA g) of the LiTiO/C nanohybrid have been significantly improved. The enhanced electrochemical performance is due to the unique structure feature, where the supersmall LTO nanoparticles are homogeneously embedded in the continuous carbon matrix. Good tap density is also achieved with the LTO/C nanohybrid due to its hierarchical micro-/nanohybrid structure, which is even higher than that of the commercial LTO powder.

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Nanostructured lithium titanate and lithium titanate/carbon nanocomposite as anode materials for advanced lithium-ion batteries

Cited by 20 publications

References 105 publications

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Structural and Electrochemical Characteristics of Ca-Doped “Flower-like” Li₄Ti₅O₁₂Motifs as High-Rate Anode Materials for Lithium-Ion Batteries

Scalable in Situ Synthesis of Li₄Ti₅O₁₂/Carbon Nanohybrid with Supersmall Li₄Ti₅O₁₂Nanoparticles Homogeneously Embedded in Carbon Matrix

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Nanostructured lithium titanate and lithium titanate/carbon nanocomposite as anode materials for advanced lithium-ion batteries

Cited by 20 publications

References 105 publications

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Analysis of Germanium Nanoparticle Composites with an Aluminum Current Collector toward Li-ion Battery Anodes with High Capacity and Broad Potential Stability Range

Structural and Electrochemical Characteristics of Ca-Doped “Flower-like” Li4Ti5O12Motifs as High-Rate Anode Materials for Lithium-Ion Batteries

Scalable in Situ Synthesis of Li4Ti5O12/Carbon Nanohybrid with Supersmall Li4Ti5O12Nanoparticles Homogeneously Embedded in Carbon Matrix

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Structural and Electrochemical Characteristics of Ca-Doped “Flower-like” Li₄Ti₅O₁₂Motifs as High-Rate Anode Materials for Lithium-Ion Batteries

Scalable in Situ Synthesis of Li₄Ti₅O₁₂/Carbon Nanohybrid with Supersmall Li₄Ti₅O₁₂Nanoparticles Homogeneously Embedded in Carbon Matrix