The Influences of Excess Sodium on Low‐Temperature Na<scp>SICON</scp> Synthesis

Bell, Nelson S.; Edney, Cynthia; Wheeler, James O.; Ingersoll, David; Spoerke, Erik David

doi:10.1111/jace.13167

Cited by 44 publications

(29 citation statements)

References 33 publications

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“…55 Using excess Na and P resources in the reactants is helpful in mitigating this problem. 56 To realize their large-scale applications, decreasing the sintering temperature is necessary. The sol-gel approach can reduce the processing temperature to some extent owing to the uniform mixing of reactants at molecular level and decreased mass transfer path.…”

Section: Nasicon Electrolytementioning

confidence: 99%

Electrolyte and Interface Engineering for Solid-State Sodium Batteries

Lü

Liu

Zhang

et al. 2018

Joule

416

340

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Sodium batteries are considered as promising candidates for large-scale energystorage systems owing to the abundant and low-cost sodium resources. However, many reported sodium batteries are based on conventional organic liquid electrolyte, which would lead to potential safety issues. Developing solid-state electrolyte (SSE) for sodium batteries is an effective way to solve such problems. Nevertheless, how to develop high-performance SSE and compatible interface for constructing solid-state sodium batteries is still challenging. In this review, we mainly focus on the development and recent advances of SSE (including all-solid-state and quasisolid-state electrolyte) and interface engineering for sodium batteries. The structure-property correlations and design principles of different inorganic and organic SSE are discussed in depth. The comprehensive performance of SSE depends on the structural characteristics such as defects, crystallinity, and stability of bonds. The design principles mainly include increasing the density of mobile Na + ions, reducing the energy barrier, immobilizing anions, adjusting the stability of bonds, adding specific buffer layers, and increasing interfacial contact area. Moreover, we discuss the interface between SSE and electrode because a suitable interface is the key prerequisite for high-performance solid-state sodium batteries. This review provides fundamental insights and future perspectives to design advanced SSE and concomitant interface for next-generation rechargeable solid-state sodium batteries.

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Section: Nasicon Electrolytementioning

confidence: 99%

Electrolyte and Interface Engineering for Solid-State Sodium Batteries

Lü

Liu

Zhang

et al. 2018

Joule

416

340

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“…1, whereas the actual peaks may shift slightly owing to solid solution and strain effects. ZrO 2 is a commonly observed impurity in NaSICon powders, 22 ceramics, [23][24][25] and films 14 and a broad peak consistent with tetragonal ZrO 2 is observed at~30.2°in 2h. The intensity of the ZrO 2 secondary phase appears to scale with increasing silicon content as it is hardly noticeable in the x = 0.25 composition and becomes more prevalent in the x = 0.75 and x = 1 compositions.…”

Section: Methodsmentioning

confidence: 99%

Scaling Effects in Sodium Zirconium Silicate Phosphate (Na₁₊_xZr₂Si_xP₃₋_xO₁₂) Ion‐Conducting Thin Films

et al. 2016

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Preparation of sodium zirconium silicate phosphate (NaSICon), Na 1+x Zr 2 Si x P 3 -x O 12 (0.25 ≤ x ≤ 1.0), thin films has been investigated via a chemical solution approach on platinized silicon substrates. Increasing the silicon content resulted in a reduction in the crystallite size and a reduction in the measured ionic conductivity. Processing temperature was also found to affect microstructure and ionic conductivity with higher processing temperatures resulting in larger crystallite sizes and higher ionic conductivities. The highest room temperature sodium ion conductivity was measured for an x = 0.25 composition at 2.3 3 10 -5 S/cm. The decreasing ionic conductivity trends with increasing silicon content and decreasing processing temperature are consistent with grain boundary and defect scattering of conducting ions.

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“…Among different sodium ion based SSEs, NA Super‐Ionic CONductor (NASICON) with a general formula of Na 1+ n Zr 2 Si n P 3− n O 12 (1.6 ≤ n ≤ 2.4), has gained the most attention due to its high ionic conductivity and low thermal expansion. [ 11–18 ] The NASICON structure, first reported by Goodenough et al, [ 19 ] consists of a rigid 3D network with P/SiO 4 tetrahedral and ZrO 6 octahedral sharing the corners. The interconnected channels of the framework serve as the conduction pathway for Na + ions ( Figure a).…”

Section: Introductionmentioning

confidence: 99%

Origin of High Ionic Conductivity of Sc‐Doped Sodium‐Rich NASICON Solid‐State Electrolytes

Sun

Xiang

Sun

et al. 2021

Adv Funct Materials

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Substitution of liquid electrolyte with solid‐state electrolytes (SSEs) has emerged as a very urgent and challenging research area of rechargeable batteries. NASICON (Na3Zr2Si2PO12) is one of the most potential SSEs for Na‐ion batteries due to its high ionic conductivity and low thermal expansion. It is proven that the ionic conductivity of NASICON can be improved to 10−3 S cm−1 by Sc‐doping, of which the mechanism, however, has not been fully understood. Herein, a series of Na3+xScxZr2−xSi2PO12 (0 ≤ x ≤ 0.5) SSEs are prepared. To gain a deep insight into the ion transportation mechanism, synchrotron‐based X‐ray absorption spectroscopy (XAS) is employed to characterize the electronic structure, and solid‐state nuclear magnetic resonance (SS‐NMR) is used to analyze the dynamics. In this study, Sc is successfully doped into Na3Zr2Si2PO12 to substitute Zr atoms. The redistribution of sodium ions at certain specific sites is proven to be critical for sodium ion movement. For x ≤ 0.3, the promotion of sodium ion movement is attributed to sodium ion concentration increase at the Na2 sites and decrease at the Na1 and Na3 sites. For x > 0.3, the inhibition of sodium ion movement is due to the phase change from monoclinic to rhombohedral and an increasing impurity content.

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The Influences of Excess Sodium on Low‐Temperature NaSICON Synthesis

Cited by 44 publications

References 33 publications

Electrolyte and Interface Engineering for Solid-State Sodium Batteries

Electrolyte and Interface Engineering for Solid-State Sodium Batteries

Scaling Effects in Sodium Zirconium Silicate Phosphate (Na₁₊_xZr₂Si_xP₃₋_xO₁₂) Ion‐Conducting Thin Films

Origin of High Ionic Conductivity of Sc‐Doped Sodium‐Rich NASICON Solid‐State Electrolytes

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The Influences of Excess Sodium on Low‐Temperature NaSICON Synthesis

Cited by 44 publications

References 33 publications

Electrolyte and Interface Engineering for Solid-State Sodium Batteries

Electrolyte and Interface Engineering for Solid-State Sodium Batteries

Scaling Effects in Sodium Zirconium Silicate Phosphate (Na1+xZr2SixP3−xO12) Ion‐Conducting Thin Films

Origin of High Ionic Conductivity of Sc‐Doped Sodium‐Rich NASICON Solid‐State Electrolytes

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Product

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Scaling Effects in Sodium Zirconium Silicate Phosphate (Na₁₊_xZr₂Si_xP₃₋_xO₁₂) Ion‐Conducting Thin Films