Mechanisms of Ionic Diffusion and Stability of the Na4MnCr(PO4)3 Cathode

Liu, Jiahui; Wang, Shuo; Sun, Qiang

doi:10.1021/acsmaterialslett.2c00194

Cited by 17 publications

(10 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…After constructing each configuration of each phase, DFT calculations were employed to obtain the configuration of the lowest energies. Then, the formation energies of HexC28 and HexC46 were calculated according to the expression below (8) where E Na C x y is the total energy of the fully sodiated structures. During the sodiation process, we can ignore the small contribution effect of volume, pressure, and entropy, where the average voltage V of the intermediate phases in the range (x 1 , x 2 ) (0 ≤ x 1 < x 2 ≤ x) can be computed using the formula below Na HexC ( ) Na HexC ( ) Na…”

Section: C ( )mentioning

confidence: 99%

“…The well-developed cobalt-free cathodes of high voltage and the wide range of sodium-based electrolytes make NIBs practically feasible and competitive with LIBs. − However, the low storage capacity of the most commonly applied anodes, such as graphite and hard carbon (HC), is a major challenge in developing advanced NIBs . In recent years, carbonaceous materials underwent immense investigation as potential and inexpensive negative electrodes for NIBs .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Design of Three-Dimensional Metallic Biphenylene Networks for Na-Ion Battery Anodes with a Record High Capacity

Obeid

et al. 2022

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

Na-ion batteries (NIBs) capture intensive research interest in large-scale energy storage applications because of sodium’s abundant resources and low cost. However, the low capacity, poor conductivity, and short cycle life of the commonly used anodes are the main challenges in developing advanced NIBs. Here, stimulated by the recent successful synthesis of biphenylene [Science 2021, 372, 852], we show that these problems can be curbed by assembling armchair biphenylene nanoribbons of different widths into three-dimensional architectures, which lead to homogeneously distributed nanopores with robust structural and mechanical stability. Through density functional theory and molecular dynamics calculations combined with the tight-binding model, we find that the assembled 3D biphenylene structures are metallic and thermally stable up to 2500 K, where the metallicity is further identified to originate from the pz-orbitals (π-bonds) of the sp2 carbon atoms. Especially, the optimal assembled structures HexC28 (HexC46) deliver a gravimetric capacity of 956 (1165) mA h g–1 and a volumetric capacity of 1109 (874) mA h mL–1, which are much higher than those of graphite and hard carbon anodes. Moreover, they also show a suitable average potential, negligible volume change, and low diffusion energy barrier. These findings demonstrate that assembling biphenylene nanoribbons is a promising strategy for designing next-generation NIB anodes.

show abstract

Section: C ( )mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Design of Three-Dimensional Metallic Biphenylene Networks for Na-Ion Battery Anodes with a Record High Capacity

Obeid

et al. 2022

ACS Appl. Mater. Interfaces

Self Cite

View full text Add to dashboard Cite

show abstract

“…To set the Ca 2+ migration path within the framework, we relaxed the initial and final end point configurations, assuming a vacancy-mediated migration mechanism, until the atomic forces were converged to |0.03| eV/Å. We considered all Ca migration events in all Ca-NaSICONs to occur between a Ca1 site and a Ca2 site within the hexagonal-prism displayed in Figure d, given previous studies that have established Na migration events to occur between Na1 and Na2 sites in Na-containing NaSICONs. , The minimum energy path (MEP) was initialized by linearly interpolating the lattice vectors and atomic positions to create seven intermediate images between the end points, with a spring constant of 5 eV per Å between images. The NEB calculation, done on Γ-centered Monkhorst-pack meshes with a density of at least 32 points per Å, was considered converged if the band forces became less than |0.05| eV/Å.…”

Section: Methodsmentioning

confidence: 99%

Exploration of NaSICON Frameworks as Calcium-Ion Battery Electrodes

et al. 2022

View full text Add to dashboard Cite

The development of energy storage technologies that are alternative to state-of-the-art lithium-ion batteries but exhibit similar energy densities, lower cost, and better safety is an important step in ensuring a sustainable energy future. Electrochemical systems based on calcium (Ca)-intercalation or deintercalation form such an alternative energy storage technology but require the development of intercalation electrode materials that exhibit reversible Ca-exchange with reasonable energy density and power density performance. To address this issue, we use first-principles calculations to screen over the wide chemical space of sodium superionic conductor (NaSICON) frameworks, with a chemical formula of Ca x M2(ZO4)3 (where M = Ti, V, Cr, Mn, Fe, Co, or Ni and Z = Si, P, or S) for Ca electrode materials. We calculate the average Ca2+ intercalation voltage, the thermodynamic stability (at 0 K) of charged and discharged Ca-NaSICON, and the migration barriers of (meta)stable Ca-NaSICON compositions. Importantly, our calculations indicate Ca x V2(PO4)3, Ca x Mn2(SO4)3, and Ca x Fe2(SO4)3 Ca-NaSICONs to be promising as Ca-cathodes. We find all silicate Ca-NaSICONs to be thermodynamically unstable and hence unsuitable as Ca-cathodes. We report the overall trends in the ground state Ca-vacancy configurations, besides voltages, stabilities, and migration barriers. Our work contributes to unearthing strategies for developing practical calcium-ion batteries, involving polyanionic intercalation frameworks.

show abstract

“…2a, which suggests that the NASICON especially environment-friendly V-free SIB electrodes have attracted great and fast-growing interest. Typical V-free NASICON cathode materials like Na 4 MnCr(PO 4 ) 3 , 34 Na 3 Fe 2 (PO 4 ) 3 , 35 and Na 3 MnTi(PO 4 ) 3 , 36 have been studied extensively, and some electrochemical properties even exceed that of the V-containing NASICON cathodes. NaTi 2 (PO 4 ) 3 with a NASICON structure is gaining increased attention as a promising anode material due to its low cost, ‘zero stress’ framework, large theoretical capacity (133 mA h g −1 ) and high Na-ion conductivity.…”

Section: Introductionmentioning

confidence: 99%