Sc, Ge co-doping NASICON boosts solid-state sodium ion batteries' performance

Composite electrolytes (CE) combining a ceramic filler and a polymer matrix is an effective way to enhance battery safety. But the increased ceramic filler mass fraction decreases the flexibility, which increases the interfacial resistance. To alleviate interfacial resistance further, a gradient composite electrolyte (GCE) using a Sc, Ge-doped Na 3 Zr 2 Si 2 PO 12 (NZSP) as the ceramic filler and poly(ethylene oxide) (PEO) as the polymer matrix is proposed. The outer layer contains a low concentration of ceramic filler to improve interfacial contact, and the central layer contains a high concentration of ceramic filler to inhibit dendrite penetration. This GCE possesses an enhanced conductivity (4.0 × 10 −5 S cm −1 at 30 °C) and a reduced interfacial resistance. Furthermore, the safety was boosted using Sn 4 P 3 @CNT/C as the high-capacity anode active material and Na 3 V 2 (PO 4 ) 3 (NVP) as the cathode active material. This ultrasafe sodium metal-free, solid-state sodium-ion battery (SSSIB) displays an impressive cycling performance.

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“…Solid-state reaction was adopted to synthesize Sc, Ge-doped NZSP powder . NVP was synthesized according to the reported study .…”

Section: Methodsmentioning

confidence: 99%

“…Solid-state reaction was adopted to synthesize Sc, Ge-doped NZSP powder. 40 NVP was synthesized according to the reported study. 39 Sn 4 P 3 @CNT/C was prepared via a hydrothermal reaction, followed by a sintering process based on the previous report.…”

Section: ■ Conclusionmentioning

confidence: 99%

Stable Interfaces in a Sodium Metal-Free, Solid-State Sodium-Ion Battery with Gradient Composite Electrolyte

Ran

Tao

Gentle

et al. 2021

ACS Appl. Mater. Interfaces

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“…Some of these attempts were already illustrated above. Other successful examples include Sc‐ and Ge‐codoped Na 3.125 Zr 1.75 Sc 0.125 Ge 0.125 Si 2 PO 12 , [ 92 ] and Sc 3+ and Yb 3+ codoped Na 3.33 Zr 1.67 Sc 0.29 Yb 0.04 Si 2 PO 12 . [ 93 ] High conductivities of 4.6 × 10 −3 and 1.5 × 10 −3 S cm −1 were achieved in these two systems, respectively.…”

Section: Structure Of Nasicon Solid Electrolytesmentioning

confidence: 99%

NaSICON: A promising solid electrolyte for solid‐state sodium batteries

Liu

et al. 2022

Interdisciplinary Materials

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A surge of interest has been brought to all-solid-state batteries (ASSBs) as they show great prospects for enabling higher energy density and improved safety compared to conventional liquid batteries. Na Super Ionic CONductors (NaSICONs) proposed by Goodenough and Hong in 1976 are the most promising materials class for Nabased ASSBs owing to their excellent ion conductivity (>1 mS cm −1 ), high thermal and chemical/electrochemical stability, as well as good chemical/electrochemical compatibility with electrode materials. The major challenge facing NaSICONtype electrolytes is the generally high interfacial resistance and thus sluggish charge transfer kinetics across the NaSICON/cathode interface. Great endeavors in the past few years have led to progress in the improvement of the ion-conducting property, and a dramatic decrease in the NaSICON/electrode interface resistance. Excellent cycling performance and rate capability have been achieved through interface engineering. In this review article, we summarize the state-of-theart findings for various derivatives of NaSICON structured solid electrolytes, with the aim of providing a deeper understanding of the underlying mechanism for the improvement of ion conductivity, and the intrinsic reasons for the enhanced interface charge transfer kinetics. These strategies can be readily extended to other solid electrolytes. We hope this review will inspire more work on NaSICONtype solid electrolytes and solid-state batteries.

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“…Whereas, the grain boundary conductivity is governed by the density and microstructures (porosity, size of grains, and grain boundaries, presence/absence of microcracks). Improved ionic conductivities of NZSP were obtained by substitution of Zr 4+ ions with aliovalent cations (e.g., Ni 2+ , Co 2+ , Zn 2+ , Mg 2+ , Ca 2+ , Al 3+ , Fe 3+ , Y 3+ , Sc 3+ , Yb 3+ , La 3+ , Nd 3+ , Nb 5+ ) and/or equivalent cations (e.g., Ce 4+ , Ti 4+ , Sn 4+ , Ge 4+ ) [6][7][8][9][10][11][12][13][14] . Besides, different synthesis strategies, such as solid-state reaction (SSR) 15,16 , solution-assisted SSR (SA-SSR) 17 , solgel 18 , coprecipitation 19 , mechanochemical 20 , and combustion method, 21 were employed to prepare NZSP.…”

Section: Introductionmentioning

confidence: 99%

High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries

et al. 2022

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Sodium superionic conductor Na3Zr2Si2PO12 (NZSP) is a promising material as a solid electrolyte for sodium‐ion batteries. The highest conductivity of ∼1.0 mS/cm at room temperature (RT) was reported for the compound with a Na content of approximately 3.3 per formula unit (f. u.) and when the material is synthesized with a final sintering temperature ≥1220°C. Herein, we propose a new synthesis method to enhance the conductivity of the NZSP by liquid‐phase sintering with the optimum amount of additive of amorphous‐Na2Si2O5. In this regard, a series of composite materials were prepared by mixing Na3Zr2Si2PO12 with amorphous‐Na2Si2O5 (NZSP/NS‐x wt.%; with x = 0.0, 2.5, 5.0, 7.5, 10.0) and sintering at a lower temperature of 1150°C. Enhanced conductivity of 1.7 mS/cm at RT has been achieved for the Na3Zr2Si2PO12/Na2Si2O5‐5.0 wt.% (NZSP/NS‐5.0) composite. The effects of additives on the NZSP phase formation, microstructure, and ion conductivity have been investigated by XRD, MAS NMR, SEM, and impedance spectroscopy. Our study demonstrates that the higher conductivity of the NZSP/NS‐5.0 composite is caused by the combined effect of increased Na content in the NZSP phase (by diffusion of Na+ ions from the liquid phase of NS to bare NZSP phase), higher density, and microstructures with lesser pores.

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Sc, Ge co-doping NASICON boosts solid-state sodium ion batteries' performance

Cited by 65 publications

References 52 publications

Stable Interfaces in a Sodium Metal-Free, Solid-State Sodium-Ion Battery with Gradient Composite Electrolyte

Stable Interfaces in a Sodium Metal-Free, Solid-State Sodium-Ion Battery with Gradient Composite Electrolyte

NaSICON: A promising solid electrolyte for solid‐state sodium batteries

High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries

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Sc, Ge co-doping NASICON boosts solid-state sodium ion batteries' performance

Cited by 65 publications

References 52 publications

Stable Interfaces in a Sodium Metal-Free, Solid-State Sodium-Ion Battery with Gradient Composite Electrolyte

Stable Interfaces in a Sodium Metal-Free, Solid-State Sodium-Ion Battery with Gradient Composite Electrolyte

NaSICON: A promising solid electrolyte for solid‐state sodium batteries

High Na+ conducting Na3Zr2Si2PO12/Na2Si2O5 composites as solid electrolytes for Na+ batteries

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High Na⁺ conducting Na₃Zr₂Si₂PO₁₂/Na₂Si₂O₅ composites as solid electrolytes for Na⁺ batteries