Lithium electrochemical deintercalation from O2-LiCoO2: structural study and first principles calculations

2002 ◽  
Vol 756 ◽  
Author(s):  
D. Carlier ◽  
A. Van der Ven ◽  
G. Ceder ◽  
L. Croguennec ◽  
M. Ménétrier ◽  
...  
Keyword(s):  
Phase Transformations ◽  
Density Functional ◽  
Driving Forces ◽  
Charge Ordering ◽  
Ionic Exchange ◽  
Two Phase ◽  
Entropy Maximization ◽  
Vacancy Ordering ◽  
Voltage Curve ◽  
Ordered Phases

ABSTRACTWe present a detailed study of the O2-LiCoO2 phase used as positive electrode in lithium batteries. This phase is a metastable form of LiCoO2 and is prepared by ionic exchange from P2-Na0.70CoO2. The O2-LiCoO2 system presents interesting fundamental problems as it exhibits several phase transformations upon lithium deintercalation that imply either CoO2 sheet gliding or lithium/vacancy ordering. Two unusual structures are observed: T#2 and O6. The T#2 phase was characterized by X-ray, neutron and electron diffraction, whereas the O6 phase was only characterized by XRD.In order to better understand the structures and the driving forces responsible for the phase transformations involved in lithium deintercalation, we combine our experimental study of this system with a theoretical approach. The voltage-composition curve at room temperature is calculated using Density Functional Theory combined with Monte Carlo simulations, and is qualitatively in good agreement with the experimental voltage curve over the complete lithium composition range. Pseudopotential and thermodynamic calculations both show that two tetrahedral sites have to be considered for Li in the T#2 structure. The calculated voltage curve thus exhibits a two-phase O2/T#2 region that indicates that this phase transformation is driven by the entropy maximization and not by a non-metal to metal transition. We also predict two ordered phases for Li1/4CoO2 (O2) and Li1/3CoO2 (O6) and show that the formation of the O6 phase is not related to Li staging or Co3+/Co4+ charge ordering.

scholarly journals Crystal Structure of the Intermediate Na2V2(PO4)3 Phase and Electrochemical Reaction Mechanisms in NaxV2(PO4)3 (1 ≤ x ≤ 4) System

2021 ◽  
Author(s):  
Sunkyu Park ◽  
Ziliang Wang ◽  
Zeyu Deng ◽  
Iona Moog ◽  
Pieremanuele Canepa ◽  
...  
Keyword(s):  
Phase Transition ◽  
Density Functional ◽  
Lattice Mismatch ◽  
Density Functional Theory Calculations ◽  
Charge Ordering ◽  
Phase Reaction ◽  
Two Phase ◽  
Space Groups ◽  
Cell Parameters ◽  
Positive Electrode Material

The Na-superionic-conductor (NASICON) Na3V2(PO4)3 is an important positive electrode material for Na-ion batteries. Here, we investigate the mechanisms of phase transition in NaxV2(PO4)3 (1 ≤ x ≤ 4) upon a non-equilibrium battery cycling. Unlike the widely believed two-phase reaction in Na3V2(PO4)3 – Na1V2(PO4)3 system, we determine a new intermediate Na2V2(PO4)3 phase using operando synchrotron X-ray diffraction. Density functional theory calculations further support the existence of the Na2V2(PO4)3 phase. We propose for the first time two possible crystal structures of Na2V2(PO4)3 analyzed by Rietveld refinement. The two structure models with the space groups P21/c or P2/c for the new intermediate Na2V2(PO4)3 phase show similar unit cell parameters but different atomic arrangements, including a vanadium charge ordering. As the appearance of the intermediate Na2V2(PO4)3 phase is accompanied by symmetry reduction, Na(1) and Na(2) sites split into several positions in Na2V2(PO4)3, in which one of the splitting Na(2) position is found to be a vacancy whereas the Na(1) positions are almost fully filled. The intermediate Na2V2(PO4)3 phase reduces the lattice mismatch between Na3V2(PO4)3 and Na1V2(PO4)3 phases facilitating a fast phase transition. This work paves the way for a better understanding of great rate capabilities of Na3V2(PO4)3.

Supersaturation and solute enrichment and their role in phase transformations in metal alloys

2011 ◽  
Vol 83 (5) ◽  
pp. 1085-1092 ◽  
Author(s):  
Markus Rettenmayr
Keyword(s):  
Phase Transformation ◽  
Phase Transformations ◽  
Single Phase ◽  
Driving Forces ◽  
Secondary Phase ◽  
Transformation Process ◽  
Primary Phase ◽  
Two Phase ◽  
Phase Mixture ◽  
Phase Out

Supersaturations and depletion or enrichment of solute/solvent are known to be the driving forces for phase transformations. In the present work, a series of different experiments is presented where in a single phase or a two-phase mixture supersaturation or enrichment/depletion of solute occur in at least one of the phases. In all cases the result is a phase transformation, particularly either the precipitation of a secondary phase out of a primary phase, or the migration of the interface in a two-phase mixture. It is demonstrated that solute transport in the phase exhibiting faster kinetics controls the phase transformation process.

scholarly journals Quasi-1D XY antiferromagnet Sr2Ni(SeO3)2Cl2 at Sakai-Takahashi phase diagram

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
E. S. Kozlyakova ◽  
A. V. Moskin ◽  
P. S. Berdonosov ◽  
V. V. Gapontsev ◽  
S. V. Streltsov ◽  
...  
Keyword(s):  
Phase Diagram ◽  
Long Range ◽  
Density Functional ◽  
Uniaxial Anisotropy ◽  
Exchange Interactions ◽  
Spin Liquid ◽  
Functional Theory ◽  
One Dimensional ◽  
Ordered Phases ◽  
Experimental Findings

AbstractUniform quasi-one-dimensional integer spin compounds are of interest as a potential realization of the Haldane conjecture of a gapped spin liquid. This phase, however, has to compete with magnetic anisotropy and long-range ordered phases, the implementation of which depends on the ratio of interchain J′ and intrachain J exchange interactions and both uniaxial D and rhombic E single-ion anisotropies. Strontium nickel selenite chloride, Sr2Ni(SeO3)2Cl2, is a spin-1 chain system which passes through a correlations regime at Tmax ~ 12 K to long-range order at TN = 6 K. Under external magnetic field it experiences the sequence of spin-flop at Bc1 = 9.0 T and spin-flip transitions Bc2 = 23.7 T prior to full saturation at Bsat = 31.0 T. Density functional theory provides values of the main exchange interactions and uniaxial anisotropy which corroborate the experimental findings. The values of J′/J = 0.083 and D/J = 0.357 place this compound into a hitherto unoccupied sector of the Sakai-Takahashi phase diagram.

scholarly journals Exploiting superspace to clarify vacancy and Al/Si ordering in mullite

IUCrJ ◽  
2018 ◽  
Vol 5 (4) ◽  
pp. 497-509 ◽  
Author(s):  
Paul Benjamin Klar ◽  
Iñigo Etxebarria ◽  
Gotzon Madariaga
Keyword(s):  
Density Functional ◽  
X Ray Diffraction ◽  
Intrinsic Structure ◽  
Functional Theory ◽  
New Approach ◽  
X Ray ◽  
Vacancy Ordering ◽  
Harmonic Modulation ◽  
First Time

Synchrotron single-crystal X-ray diffraction has revealed diffuse scattering alongside sharp satellite reflections for different samples of mullite (Al4+2xSi2−2xO10−x). Structural models have been developed in (3+1)-dimensional superspace that account for vacancy ordering and Al/Si ordering based on harmonic modulation functions. A constraint scheme is presented which explains the crystal-chemical relationships between the split sites of the average structure. The modulation amplitudes of the refinements differ significantly by a factor of ∼3, which is explained in terms of different degrees of ordering,i.e.vacancies follow the same ordering principle in all samples but to different extents. A new approach is applied for the first time to determine Al/Si ordering by combining density functional theory with the modulated volumes of the tetrahedra. The presence of Si–Si diclusters indicates that the mineral classification of mullite needs to be reviewed. A description of the crystal structure of mullite must consider both the chemical composition and the degree of ordering. This is of particular importance for applications such as advanced ceramics, because the physical properties depend on the intrinsic structure of mullite.

Contribution of different chemical groups to the driving forces for the partition of phenylmethane dyes in the PEO1500 + MgSO4 + H2O aqueous two-phase system

2020 ◽  
Vol 508 ◽  
pp. 112451
Author(s):  
Elkin Dario C. Castrillon ◽  
Yara L. Coelho ◽  
Álvaro Javier P. Agudelo ◽  
Isabela A. Marques ◽  
Eliara A. Hudson ◽  
...  
Keyword(s):  
Driving Forces ◽  
Phase System ◽  
Two Phase ◽  
Aqueous Two Phase System ◽  
Chemical Groups

Hydrocarbon-Phase Behaviors in Shale Nanopore/Fracture Model: Multiscale, Multicomponent, and Multiphase

SPE Journal ◽  
2019 ◽  
Vol 24 (06) ◽  
pp. 2526-2540 ◽  
Author(s):  
Yinuo Zhao ◽  
Zhehui Jin
Keyword(s):  
Oil Recovery ◽  
Density Functional ◽  
Critical Role ◽  
Volume Ratio ◽  
Phase Region ◽  
Bulk Phase ◽  
Two Phase ◽  
Well Productivity ◽  
Pressure Drops ◽  
Shale Reservoirs

Summary Hydrocarbon recovery from shale subformations has greatly contributed to the global energy supply and has been constantly reshaping the energy sector. Oil production from shale is a complex process in which multicomponent–fluid mixtures experience multiphase transitions in multiscale volumes (i.e., nanoscale pores are connected to fractures/macropores). Understanding such complicated phenomena plays a critical role in the estimation of ultimate oil recovery, well productivity, and reserves estimation, and ultimately in policy making. In this work, we use density–functional theory (DFT) to explicitly consider fluid/surface interactions, inhomogeneous–density distributions in nanopores, volume partitioning in nanopores, and connected macropores/natural fractures to study the complex multiphase transitions of multicomponent fluids in multiscale volumes. We found that vapor–like and liquid–like phases can coexist in nanopores when pressure is between the bubblepoint and dewpoint pressures of nanoconfined fluids, both of which are much lower than those of the originally injected hydrocarbon mixtures. As the volume ratio of the bulk at the initial condition to pores decreases, both the bubblepoint and the dewpoint in nanopores increase and the pore two–phase region expands. Within the pore two–phase region, both C1 and C3 are released from the nanopores to the bulk phase as pressure declines. Meanwhile, both liquid and vapor phases become denser as pressure drops. By further decreasing pressure below the dewpoint of confined fluids, C3 in the nanopore can be recovered. Throughout the process, the bulk–phase composition varies, which is in line with the field observation. Collectively, this work captures the coupled complexity of multicomponent and multiphase fluids in multiscale geometries that is inherent to shale reservoirs and provides a theoretical foundation for reservoir simulation, which is significant for the accurate prediction of well productivity and ultimate oil recovery in shale reservoirs.

scholarly journals Ultrafast charge ordering by self-amplified exciton–phonon dynamics in TiSe2

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Chao Lian ◽  
Sheng-Jie Zhang ◽  
Shi-Qi Hu ◽  
Meng-Xue Guan ◽  
Sheng Meng
Keyword(s):  
Density Functional ◽  
Laser Pulses ◽  
Underlying Mechanism ◽  
Charge Density Waves ◽  
Complete Separation ◽  
Charge Ordering ◽  
Periodic Lattice ◽  
Microscopic Mechanism ◽  
Time Resolved ◽  
Electron Phonon Coupling

AbstractThe origin of charge density waves (CDWs) in TiSe$${}_{2}$$2 has long been debated, mainly due to the difficulties in identifying the timescales of the excitonic pairing and electron–phonon coupling (EPC). Without a time-resolved and microscopic mechanism, one has to assume simultaneous appearance of CDW and periodic lattice distortions (PLD). Here, we accomplish a complete separation of ultrafast exciton and PLD dynamics and unravel their interplay in our real-time time-dependent density functional theory simulations. We find that laser pulses knock off the exciton order and induce a homogeneous bonding–antibonding transition in the initial 20 fs, then the weakened electronic order triggers ionic movements antiparallel to the original PLD. The EPC comes into play after the initial 20 fs, and the two processes mutually amplify each other leading to a complete inversion of CDW ordering. The self-amplified dynamics reproduces the evolution of band structures in agreement with photoemission experiments. Hence we resolve the key processes in the initial dynamics of CDWs that help elucidate the underlying mechanism.

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