Effect of In-Plane Density on the Structural and Elastic Properties of Graphite Intercalation Compounds

Woo, K. C.; Kamitakahara, W. A.; DiVincenzo, David P.; Robinson, Douglas S.; Mertwoy, H.; Milliken, J.; Fischer, J. E.

doi:10.1103/physrevlett.50.182

Cited by 87 publications

(63 citation statements)

References 13 publications

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“…The graphite intercalation stage or insertion phenomena have been studied previously [8,39,[42][43][44]. Dahn and co-workers [39,42] reported that Lonza KS 44, an artificial graphite, gave five distinguishable peaks in the slow scan differential chronopotentiograms, while three peaks were observed with Brazilian graphite in this work, although five peaks were observed with g-Fe 600-2800.…”

Section: Staging Phenomenamentioning

confidence: 82%

Novel carbon nanofibers of high graphitization as anodic materials for lithium ion secondary batteries

Yoon

Park²,

Yang

et al. 2004

Carbon

174

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Section: Staging Phenomenamentioning

confidence: 82%

Novel carbon nanofibers of high graphitization as anodic materials for lithium ion secondary batteries

Yoon

Park²,

Yang

et al. 2004

Carbon

174

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“…A further peculiarity of the Li-GICs is the existence of two distinct stage-2 phases: besides the ordered compound LiC12, which transforms above about 500 K to stage-1 with no long-range in-plane order [5], there exists a dilute compound, labeled LiC16, which has no long-range order already at room temperature [5,6]. The stage-2 compounds thus offer the possibility to examine the role of in plane ordering in diffusion.…”

Section: Introductionmentioning

confidence: 99%

Diffusive Motion in Stage-1 and Stage-2 Li-Graphite Intercalation Compounds: Results of ß-NMR and Quasielastic Neutron Scattering

Schirmer

Heitjans

1995

Zeitschrift Für Naturforschung A

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Dedicated to Professor Werner Müller-Warmuth on the occasion of his 65th birthdayInvestigations of Li diffusion in stage-1 and stage-2 Li graphite intercalation compounds with neutron time-of-flight and backscattering techniques and ^-radiation detected nuclear magnetic resonance/relaxation (/J-NMR) with the nucleus 8Li(T1/2 = 0.8 s) are reviewed and compared. De pending on temperature, the spin-lattice relaxation-rate T{1 of 8Li is governed by different pro cesses. Above 300 K, T f1 (T) shows maxima induced by long-range Li+ diffusion. Jump correlation times are estimated. Inspection of the B field dependence of T f1 revealed two-dimensional diffusion behaviour. The neutron spectra showed a quasielastic line broadening above 500 K, which was used to obtain diffusion coefficients and to trace jump vectors of the in-plane motion. The diffusion parameters observed with both techniques are compared, and differences that show up are dis cussed. In addition, the low-temperature spin-lattice relaxation rates, being due to coupling to conduction electrons, are used to explore electronic properties.

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“…Computational studies of lithiated graphite have shown that the orientation-averaged elastic modulus changes by a factor of 2-3 upon maximal lithiation, 29 and variations consistent with these calculations have been reported experimentally. 28 Similarly, reduction of elastic moduli by a factor of 2-3 has been predicted computationally for lithiated silicon alloys 32 and verified experimentally. 19,[21][22][23][24][25][26][27] Mechanical property variations of this magnitude affect the stress distributions developed in electrochemically active materials.…”

mentioning

confidence: 99%

“…Thus, the extent to which K Ic and other elastoplastic properties of ion-storage materials vary with lithium concentration, is understood poorly. 18,28,29 Identifying any such correlations will facilitate realistic application of mechanical failure models as a function of state-of-charge, and allow prediction and extension of durability and lifetime of electrode materials and devices. * Electrochemical Society Active Member.…”

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confidence: 99%

Effect of Electrochemical Charging on Elastoplastic Properties and Fracture Toughness of Li_XCoO₂

Swallow

Woodford

McGrogan

et al. 2014

J. Electrochem. Soc.

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Mechanical degradation of lithium-ion battery (LIB) electrodes has been correlated with capacity fade and impedance growth over repeated charging and discharging. Knowledge of how the mechanical properties of materials used in LIBs are affected by electrochemical lithiation and delithiation could provide insight into design choices that mitigate mechanical damage and extend device lifetime. Here, we measured Young's modulus E, hardness H, and fracture toughness K Ic via instrumented nanoindentation of the prototypical intercalation cathode, Li X CoO 2 , after varying durations of electrochemical charging. After a single charge cycle, E and H decreased by up to 60%, while K Ic decreased by up to 70%. Microstructural characterization using optical microscopy, Raman spectroscopy, X-ray diffraction, and further nanoindentation showed that this degradation in K Ic was attributable to Li depletion at the material surface and was also correlated with extensive microfracture at grain boundaries. These results indicate that K Ic reduction and irreversible microstructural damage occur during the first cycle of lithium deintercalation from polycrystalline aggregates of Li X CoO 2 , potentially facilitating further crack growth over repeated cycling. Such marked reduction in K Ic over a single charge cycle also yields important implications for the design of electrochemical shock-resistant cathode materials. Energy storage is an enabling technology for electrified transportation and for large-scale deployment of renewable energy resources such as solar and wind. For many applications, non-aqueous ionintercalation chemistries such as Li-ion are attractive for their high energy density and electrochemical reversibility. However, the electrode materials used in ion-intercalation batteries undergo significant composition changes-which correlate to high storage capacity-that can induce structural changes and mechanical stresses; these changes can degrade battery performance metrics such as power, achievable storage capacity, and lifetime.1-8 Microstructural damage has been observed directly in numerous electrode materials subjected to electrochemical cycling, both within single crystals (or grains) and among polycrystalline aggregates. 4,5,[7][8][9][10][11][12][13][14][15] While the relationships among electrode microstructure, electrochemical cycling conditions, crystallographic changes in the active materials, and resulting mechanical stresses have been elucidated, relatively little is known about the composition-dependency of the key physical properties. Numerous models have been developed to predict mechanical deformation in ion-storage materials during electrochemical cycling, as recently reviewed by Mukhopadhyay and Sheldon. 16 The quantitative utility of such models is dependent on measured elastoplastic properties, particularly the fracture toughness of these materials. To date, few experimental measurements of fracture toughness K Ic of battery materials have been reported; [17][18][19][20] similarly, few measureme...

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Effect of In-Plane Density on the Structural and Elastic Properties of Graphite Intercalation Compounds

Cited by 87 publications

References 13 publications

Novel carbon nanofibers of high graphitization as anodic materials for lithium ion secondary batteries

Novel carbon nanofibers of high graphitization as anodic materials for lithium ion secondary batteries

Diffusive Motion in Stage-1 and Stage-2 Li-Graphite Intercalation Compounds: Results of ß-NMR and Quasielastic Neutron Scattering

Effect of Electrochemical Charging on Elastoplastic Properties and Fracture Toughness of Li_XCoO₂

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Effect of In-Plane Density on the Structural and Elastic Properties of Graphite Intercalation Compounds

Cited by 87 publications

References 13 publications

Novel carbon nanofibers of high graphitization as anodic materials for lithium ion secondary batteries

Novel carbon nanofibers of high graphitization as anodic materials for lithium ion secondary batteries

Diffusive Motion in Stage-1 and Stage-2 Li-Graphite Intercalation Compounds: Results of ß-NMR and Quasielastic Neutron Scattering

Effect of Electrochemical Charging on Elastoplastic Properties and Fracture Toughness of LiXCoO2

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Effect of Electrochemical Charging on Elastoplastic Properties and Fracture Toughness of Li_XCoO₂