Influence of Nb5+, Ti4+, Y3+ and Zn2+ doped Na3Zr2Si2PO12 solid electrolyte on its conductivity

Chen, Dan; Luo, Fa; Zhou, Wancheng; Zhu, Dongmei

doi:10.1016/j.jallcom.2018.05.116

Cited by 79 publications

(36 citation statements)

References 28 publications

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“…Moreover, the occupation of Na + ‐ions at the high energy site lowers the energy barrier for ion conduction. Our theory also reveals the underlying origin for the enhancement in bulk conductivity observed in previous doped NaSICON materials, in which the Na + ‐ion concentration increases as a compenstation of the aliovalent doping (Zn 2+ , Ca 2+ , Ba 2+ , Y 3+ , Sc 3+ ) at the Zr site. In these doped NaSICON systems, the increased Na + ‐ion concentration likely invokes more correlated migration and therefore lowered the energy barrier for Na + ‐ion diffusion.…”

Section: Resultssupporting

confidence: 54%

“…Our theory also reveals the underlying origin for the enhancement in bulk conductivity observed in previous doped NaSICON materials, [27][28][29][30] in which the Na +ion concentration increases as a compenstation of the aliovalent doping (Zn 2+ , Ca 2+ , Ba 2+ , Y 3+ , Sc 3+ ) at the Zr site. This finding supports the results of theory described above, which suggests that the Na + -ion concentration is a main factor determining the bulk conductivity in NaSICON materials.…”

supporting

confidence: 57%

“…[21][22][23] The total ion conductivity varies by an order of magnitude with x and the highest value (0.67 mS cm −1 at 300 K) was reported in the monoclinic phase where x ≈ 2.0, that is, Na 3 Zr 2 Si 2 PO 12 . [28][29][30] Guin and Tietz [31] reviewed various substituted NaSICONtype materials and concluded that the optimum ion conductivity is achieved at a Na + -ion content of ≈3.3 mol formula unit −1 . Researchers have primarily focused on using doping strategies to further improve the conductivity of this system, with Sc-substituted Na 3.4 Sc 0.2 Zr 1.8 (SiO 4 ) 2 (PO 4 ) exhibiting the highest reported conductivity at room temperature (6.2 mS cm −1 for the bulk value and 4.0 mS cm −1 for the total value, respectively).…”

Section: Introductionmentioning

confidence: 99%

“…We note that the bulk conductivity could not be enhanced by threefold when the Na + ‐ion content simply increased from 3.0 to 3.4 mol formula unit −1 , based on the standard expression for ion conductivity as a function of the number of mobile carriers. Other aliovalent substitutions at the Zr site also give rise to high conductivities in the order of 10 −3 S cm −1 at room temperature . Guin and Tietz reviewed various substituted NaSICON‐type materials and concluded that the optimum ion conductivity is achieved at a Na + ‐ion content of ≈3.3 mol formula unit −1 .…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Correlated Migration Invokes Higher Na⁺‐Ion Conductivity in NaSICON‐Type Solid Electrolytes

Zhang

Zou

Kaup

et al. 2019

Advanced Energy Materials

190

223

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Na super ion conductor (NaSICON), Na 1+n Zr 2 Si n P 3-n O 12 is considered one of the most promising solid electrolytes; however, the underlying mechanism governing ion transport is still not fully understood. Here, the existence of a previously unreported Na5 site in monoclinic Na 3 Zr 2 Si 2 PO 12 is unveiled. It is revealed that Na + -ions tend to migrate in a correlated mechanism, as suggested by a much lower energy barrier compared to the single-ion migration barrier. Furthermore, computational work uncovers the origin of the improved conductivity in the NaSICON structure, that is, the enhanced correlated migration induced by increasing the Na + -ion concentration. Systematic impedance studies on doped NaSICON materials bolster this finding. Significant improvements in both the bulk and total ion conductivity (e.g., σ bulk = 4.0 mS cm −1 , σ total = 2.4 mS cm −1 at 25 °C) are achieved by increasing the Na content from 3.0 to 3.30-3.55 mol formula unit −1 . These improvements stem from the enhanced correlated migration invoked by the increased Coulombic repulsions when more Na + -ions populate the structure rather than solely from the increased mobile ion carrier concentration. The studies also verify a strategy to enhance ion conductivity, namely, pushing the cations into high energy sites to therefore lower the energy barrier for cation migration.

show abstract

Section: Resultssupporting

confidence: 54%

supporting

confidence: 57%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Correlated Migration Invokes Higher Na⁺‐Ion Conductivity in NaSICON‐Type Solid Electrolytes

Zhang

Zou

Kaup

et al. 2019

Advanced Energy Materials

190

223

View full text Add to dashboard Cite

show abstract

“…A similar effect was achieved by Ce 4+ ‐doped NZSP (Figure 7c). [ 65 ] Other ions, such as Mg 2+ , [ 66 ] Ni, [ 59 ] La 3+ , [ 67 ] Zn 2+ , [ 68 ] Y 3+ , and Nb 5+ , [ 69 ] have also been doped in NZSP, and a high ionic conductivity up to 3.4 × 10 −3 S cm −1 at RT was obtained. The similar effect can also be achieved by shifting the Si/P ratio and increasing the Na content accordingly, [ 70 ] but this has not been systematically investigated.…”

Section: Advances On Sesmentioning

confidence: 99%

Progress and Challenges for All‐Solid‐State Sodium Batteries

Yang

Zhang

Konstantinov

et al. 2021

Adv Energy and Sustain Res

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All‐solid‐state sodium batteries (ASSBs) are regarded as the next generation of sustainable energy storage systems due to the advantages of abundant sodium resources, and their exceptional and high energy density. Nevertheless, there are still grand challenges to realize their practical applications, such as the limited types of solid‐state electrolytes (SEs), low ionic conductivity of SEs, high charge‐transfer impedance, interfacial issues, and Na dendrite growth. Herein, the recent progress and challenges of various SEs for ASSBs are summarized, including solid polymer electrolytes, inorganic solid electrolytes (including oxides, sulfides, and boron hydrides), and their combinations. Furthermore, recent reports on various cathodes materials and corresponding cathode/SE interfacial issues are comprehensively reviewed. Current trends and future perspectives on sodium metal anodes are discussed in detail with an emphasis on the anode interface protection and innovative SEs with good Na compatibility. Finally, future opportunities for the development of ASSBs are outlined.

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Rethinking the Design of Ionic Conductors Using Meyer–Neldel–Conductivity Plot

Gao

et al. 2021

Advanced Energy Materials

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From the discovery of the first fast ionic conductor silver iodide in the early 20th century to the recent discovery of lithium fast ionic conductors with ionic conductivities surpassing those of liquid electrolytes, high ionic conductivity σ has often been associated with low activation energy Ea following the Arrhenius equation. However, the Meyer–Neldel rule (MNR) indicates that the Ea and prefactor σ0 are correlated, suggesting the relation between the Ea and σ is, in fact, complex. In this perspective, the use of the Meyer–Neldel–conductivity plot and a critical descriptor, Meyer–Neldel energy Δ0, to guide the search for fast ionic conductors is proposed. Reported lithium, sodium, and magnesium ionic conductors are categorized into three types, depending on the relative magnitude between the Δ0 and thermal energy (kBT) at the application temperature. The process by which σ can be optimized by tuning Ea for these types of ionic conductors is elaborated. This principle can be widely applied to all ionic conductors that obey the MNR at any application temperature. Furthermore, a pressure‐tuning approach to measure the Δ0 rapidly is developed. These findings establish a previously missing step for designing new ionic conductors with improved ionic conductivity.

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Influence of Nb5+, Ti4+, Y3+ and Zn2+ doped Na3Zr2Si2PO12 solid electrolyte on its conductivity

Cited by 79 publications

References 28 publications

Correlated Migration Invokes Higher Na⁺‐Ion Conductivity in NaSICON‐Type Solid Electrolytes

Correlated Migration Invokes Higher Na⁺‐Ion Conductivity in NaSICON‐Type Solid Electrolytes

Progress and Challenges for All‐Solid‐State Sodium Batteries

Rethinking the Design of Ionic Conductors Using Meyer–Neldel–Conductivity Plot

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Influence of Nb5+, Ti4+, Y3+ and Zn2+ doped Na3Zr2Si2PO12 solid electrolyte on its conductivity

Cited by 79 publications

References 28 publications

Correlated Migration Invokes Higher Na+‐Ion Conductivity in NaSICON‐Type Solid Electrolytes

Correlated Migration Invokes Higher Na+‐Ion Conductivity in NaSICON‐Type Solid Electrolytes

Progress and Challenges for All‐Solid‐State Sodium Batteries

Rethinking the Design of Ionic Conductors Using Meyer–Neldel–Conductivity Plot

Contact Info

Product

Resources

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Correlated Migration Invokes Higher Na⁺‐Ion Conductivity in NaSICON‐Type Solid Electrolytes

Correlated Migration Invokes Higher Na⁺‐Ion Conductivity in NaSICON‐Type Solid Electrolytes