A High‐Energy NASICON‐Type Cathode Material for Na‐Ion Batteries

Wang, Jingyang; Wang, Yan; Seo, Dong‐Hwa; Shi, Tan; Chen, Shouping; Tian, Yulin; Kim, Haegyeom; Ceder, Gerbrand

doi:10.1002/aenm.201903968

Cited by 142 publications

(156 citation statements)

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“…Lattice doping has been proven to be an effective strategy to tune the charge transfer behavior or/and working voltage of Na 3 V 2 (PO 4 ) 3 . [12][13][14] Introduction of F − with high electronegativity in phosphate sites can effectively elevate the operation voltage and thus, the energy density because of the enhanced ionicity of the anionic framework. Therefore, a new series of sodium vanadium fluorophosphate, Na 3 V 2 (PO 4 ) 2 (O 2−2x F 1+2x ) (0 ≤ x ≤1), is becoming a research hotspot due to their high energy density (≈500 W h kg −1 ), which is comparable to the value of commercial LiFePO 4 .…”

Section: Introductionmentioning

confidence: 99%

Ostwald Ripening Tailoring Hierarchically Porous Na₃V₂(PO₄)₂O₂F Hollow Nanospheres for Superior High‐Rate and Ultrastable Sodium Ion Storage

Zhao

Rong

Niu

et al. 2020

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Low cost sodium-ion batteries (SIBs), have been widely recognized as one of the competitive next-generation electrical energy-storage technologies, owing to the widespread distribution and huge abundance of sodium resources. [2,3] From the perspective of the overall energy-and costeffectiveness of SIBs, cathode material is the key component that determines the energy density, electrochemical performance, and cost. [4-6] Thus, extensive efforts have been devoted to the investigations on cathode materials to boost the commercial availability of SIBs. Compared to its lithium counterpart, the large ionic radius and heavy atomic mass of Na + leads to sluggish electrode reaction kinetics and undesirable structure degradation during repeated Na + insertion/extraction, severely limiting the electrochemical performance of SIBs. Therefore, exploiting promising cathode materials with not only high energy density but also the capabilities of fast Na + diffusion and stable cyclability is of great importance to meet the urgent requirements for practical applications. Among various cathode materials for SIBs, Na +-superionic conductor (NASICON) type compounds are intensively investigated as favorable candidates owing to their high Na + mobility, rich structural diversity, and pronounced structural Sodium-ion batteries (SIBs) are receiving considerable attention as economic candidates for large-scale energy storage applications. Na 3 V 2 (PO 4) 2 O 2 F (NVPF) is intensively regarded as one of the most promising cathode materials for SIBs, due to its high energy density, fast ionic conduction, and robust Na +-super-ionic conductor (NASICON) framework. However, poor rate capability ascribed to the intrinsically low electronic conductivity severely hinders their practical applications. Here, high-rate and highly reversible Na + storage in NVPF is realized by optimizing nanostructure and rational porosity construction. Hierarchical porous NVPF hollow nanospheres are designed to modify the issues of inconvenient electrolyte transportation and unfavorable charge transfer behavior faced by solid-structured electrode materials. The individual unique nanosphere is assembled from numerous nanoparticles, which shortens the length of Na + transport in solid state and thus facilites the Na + migration. Hollow nanostructure hierarchically porous configuration enables adequate electrolyte penetration, continuous electrolyte supplementation, and facile electrolyte transportation, leading to barrier-free Na + /e − diffusion and high-rate cycling. In addition, the large electrolyte accessible surface area boosts the charge transfer in the whole electrode. Therefore, the present NVPF demonstrates unprecedented rate capability (85.4 mAh g −1 at 50 C) and long-term cyclability (62.2% capacity retention after 2000 cycles at 20 C).

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Section: Introductionmentioning

confidence: 99%

Ostwald Ripening Tailoring Hierarchically Porous Na₃V₂(PO₄)₂O₂F Hollow Nanospheres for Superior High‐Rate and Ultrastable Sodium Ion Storage

Zhao

Rong

Niu

et al. 2020

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“…62,63 The exchange-correlation energy in DFT was approximated by the strongly constrained and appropriately normed (SCAN) semi-local metageneralized gradient approximation (GGA) functional. 64 The accuracy of SCAN has been demonstrated on oxides and phosphates, [65][66][67] where SCAN has been shown not to overbind O 2 gas, as is typical in GGA functionals. 68 Wavefunctions were expanded in terms of a plane-wave basis set, truncated at a kinetic energy cut-off of 520 eV and combined with projector augmented-wave (PAW) potentials to describe the core electrons.…”

Section: Details Of Monte Carlo Cluster Expansion and Dft Calculationsmentioning

confidence: 95%

Phase Behavior in Nasicon Electrolytes and Electrodes

et al. 2020

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An avenue to create safer batteries is to replace the liquid electrolyte with a non-flammable solid electrolyte.1–3 A good candidate is the Natrium superionic conductor (NaSiCON) Na1+xZr2SixP3-xO12 (0 x 3) which displays high bulk ionic conductivity and good relative stability towards other NaSiCON-based electrodes.2 Despite the sizeable share of research on the Na1+xZr2SixP3-xO12 material, the structural properties of NaSiCON are still poorly understood and as a result the optimisation of this class of materials often follows chemical intuition.4–9 Here, we analyse the phase behaviour of the NaSiCON electrolyte by constructing the Na1+xZr2SixP3-xO12 phase diagram as a function of temperature and composition (0 x 3) for the high-temperature rhombohedral phase. This phase is also common in several Na-based positive electrodes, such as Na3Ti2(PO4)3, Na3V2(PO4)3 and Na3Cr2(PO4)3. Using a multi-scale approach, based on density functional theory, the cluster expansion formalism and Monte Carlo simulations, we elucidate: i) the entire phase-diagram of NaSiCON as a function of temperature and Na content, identifying the regions providing the highest Na+-ion conductivity; ii) previously, unreported phase-separation behaviour in a specific region of the phase diagram, iii) the relationship between the population of Na-sites and the relative ratio of Si:P in the structure. We reveal that kinetic effects hinder the expected mechanism of phase separation in Na1+xZr2SixP3-xO12. We then extended these principles between the competition of thermodynamic and kinetic driving forces derived on Na1+xZr2SixP3-xO12 to popular mono-transition metal NaSiCON electrodes, which all tend to phase separate upon Na extraction/insertion. These results are important for the development of inexpensive Na-ion batteries. (1) Janek, J.; Zeier, W. G. A Solid Future for Battery Development. Nature Energy 2016, 1 (9), 16141. https://doi.org/10.1038/nenergy.2016.141. (2) Famprikis, T.; Canepa, P.; Dawson, J. A.; Islam, M. S.; Masquelier, C. Fundamentals of Inorganic Solid-State Electrolytes for Batteries. Nat. Mater. 2019, 18, 1278–1291. https://doi.org/10.1038/s41563-019-0431-3. (3) Canepa, P.; Dawson, J. A.; Sai Gautam, G.; Statham, J. M.; Parker, S. C.; Islam, M. S. Particle Morphology and Lithium Segregation to Surfaces of the Li7La3Zr2O12 Solid Electrolyte. Chemistry of Materials 2018, 30 (9), 3019–3027. https://doi.org/10.1021/acs.chemmater.8b00649. (4) Hong, H. Y.-P. Crystal Structures and Crystal Chemistry in the System Na1+xZr2SixP3−xO12. Materials Research Bulletin 1976, 11 (2), 173–182. https://doi.org/10.1016/0025-5408(76)90073-8. (5) Boilot, J. P.; Collin, G. Relation Structure-Fast Ion Conduction in the NASICON Solid Solution. J. Solid State Chem. 1988, 73, 160–171. (6) Masquelier, C.; Croguennec, L. Polyanionic (Phosphates, Silicates, Sulfates) Frameworks as Electrode Materials for Rechargeable Li (or Na) Batteries. Chem. Rev. 2013, 113 (8), 6552–6591. https://doi.org/10.1021/cr3001862. (7) Ma, Q.; Guin, M.; Naqash, S.; Tsai, C.-L.; Tietz, F.; Guillon, O. Scandium-Substituted Na3Zr2(SiO4)2(PO4) Prepared by a Solution-Assisted Solid-State Reaction Method as Sodium-Ion Conductors. Chemistry of Materials 2016, 28 (13), 4821–4828. https://doi.org/10.1021/acs.chemmater.6b02059. (8) Deng, Y.; Eames, C.; Nguyen, L. H. B.; Pecher, O.; Griffith, K. J.; Courty, M.; Fleutot, B.; Chotard, J.-N.; Grey, C. P.; Islam, M. S.; Masquelier, C. Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes. Chem. Mater. 2018, 30 (8), 2618–2630. https://doi.org/10.1021/acs.chemmater.7b05237. (9) Zhang, Z.; Zou, Z.; Kaup, K.; Xiao, R.; Shi, S.; Avdeev, M.; Hu, Y.-S.; Wang, D.; He, B.; Li, H.; Huang, X.; Nazar, L. F.; Chen, L. Correlated Migration Invokes Higher Na+-Ion Conductivity in NaSICON-Type Solid Electrolytes. Advanced Energy Materials 2019, 9 (42), 1902373. https://doi.org/10.1002/aenm.201902373.

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“…Cr-Mn [31,37] R-3c Among the NaxM2(PO4)3 compounds, NaxCr2(PO4)3 delivers the highest measured voltage of ~4.5 V (~4 V calculated theoretically) vs. Na/Na + , [49] albeit with a limited capacity of just ~98 mAh/g, and corresponding to the extraction of 2 Na from Na3Cr III Cr III (PO4)3 to form Na1Cr IV Cr III (PO4)3. Indeed, Na4Cr2(PO4) 3 has not yet been obtained by either a chemical or an electrochemical process.…”

Section: Theo Capacitymentioning

confidence: 99%

A Chemical Map of NaSiCON Electrode Materials for Sodium-ion Batteries

Gill¹,

Wang²,

Park³

et al. 2020

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<div><div><div><p>Na-ion batteries are promising devices for smart grids and electric vehicles due to cost effectiveness arising from the overall abundance of sodium (Na) and its even geographical distribution. Among other factors, the energy density of Na-ion batteries is limited by the positive electrode chemistry. NaSICON-based positive electrode materials are known for their wide range of electrochemical potentials,[1],[2],[3] high ionic conductivity, and most importantly their structural and thermal stabilities. Using first- principles calculations, we chart the chemical space of 3d transition metal-based NaSICON phosphates of formula NaxMM’(PO4)3 (with M and M’= Ti, V, Cr, Mn, Fe, Co and Ni), to analyze their thermodynamic stabilities and the intercalation voltages for Na+ ions. Specifically, we computed the Na insertion voltages and related properties of 28 distinct NaSICON compositions. We investigated the thermodynamic stability of Na-intercalation in previously unreported NaxMn2(PO4)3 and NaxVCo(PO4)3. The calculated quaternary phase diagrams of the Na-P-O-Co and Na-P-O-Ni chemical systems explain the origin of the suspected instability of Ni and Co-based NaSICON compositions. From our analysis, we are also able to rationalize anomalies in previously reported experimental data in this diverse and important chemical space.</p></div></div></div>

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A High‐Energy NASICON‐Type Cathode Material for Na‐Ion Batteries

Cited by 142 publications

References 71 publications

Ostwald Ripening Tailoring Hierarchically Porous Na₃V₂(PO₄)₂O₂F Hollow Nanospheres for Superior High‐Rate and Ultrastable Sodium Ion Storage

Ostwald Ripening Tailoring Hierarchically Porous Na₃V₂(PO₄)₂O₂F Hollow Nanospheres for Superior High‐Rate and Ultrastable Sodium Ion Storage

Phase Behavior in Nasicon Electrolytes and Electrodes

A Chemical Map of NaSiCON Electrode Materials for Sodium-ion Batteries

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A High‐Energy NASICON‐Type Cathode Material for Na‐Ion Batteries

Cited by 142 publications

References 71 publications

Ostwald Ripening Tailoring Hierarchically Porous Na3V2(PO4)2O2F Hollow Nanospheres for Superior High‐Rate and Ultrastable Sodium Ion Storage

Ostwald Ripening Tailoring Hierarchically Porous Na3V2(PO4)2O2F Hollow Nanospheres for Superior High‐Rate and Ultrastable Sodium Ion Storage

Phase Behavior in Nasicon Electrolytes and Electrodes

A Chemical Map of NaSiCON Electrode Materials for Sodium-ion Batteries

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Product

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Ostwald Ripening Tailoring Hierarchically Porous Na₃V₂(PO₄)₂O₂F Hollow Nanospheres for Superior High‐Rate and Ultrastable Sodium Ion Storage

Ostwald Ripening Tailoring Hierarchically Porous Na₃V₂(PO₄)₂O₂F Hollow Nanospheres for Superior High‐Rate and Ultrastable Sodium Ion Storage