Characterization of hot-pressed von Alpen type NASICON ceramic electrolytes

Valle, Joseph; Huang, Claire; Tatke, Dhruv; Wolfenstine, J.; Go, Wooseok; Kim, Young‐Sik; Sakamoto, Jeff

doi:10.1016/j.ssi.2021.115712

Cited by 18 publications

(18 citation statements)

References 55 publications

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“…R HF is the sum of Ohmic series resistances of the current collector, NaSICON pellet and liquid electrolyte, whereas R GB originates from Na + transport through grain boundaries, i.e., between the grains and glassy phase. The latter attribution is supported from fitting EIS measurements made on symmetric Au|NaSICON|Au cells (Figure S5a) to the modified equivalent circuit proposed by Huggins (Figure S5b ) , which is a well-established model for NaSICON . Capacitances for R GB in Figure S5a are within the 10 –8 –10 –9 F/cm 2 range and are consistent with the range of literature values for the capacitance of the grain boundary (10 –11 –10 –8 F/cm 2 ), as opposed to that of the macroscopic interface between the pellet and electrolyte or current collector, which is expected to be in the 10 –7 –10 –5 F/cm 2 range .…”

Section: Resultssupporting

confidence: 82%

“…The latter attribution is supported from fitting EIS measurements made on symmetric Au|NaSICON|Au cells (Figure S5a) to the modified equivalent circuit proposed by Huggins 39 (Figure S5b), which is a wellestablished model for NaSICON. 31 Capacitances for R GB in Figure S5a are within the 10 −8 −10 −9 F/cm 2 range and are consistent with the range of literature values for the capacitance of the grain boundary (10 −11 −10 −8 F/cm 2 ), as opposed to that of the macroscopic interface between the pellet and electrolyte or current collector, which is expected to be in the 10 −7 −10 −5 F/ cm 2 range. 40 The capacitances corresponding to the semicircles in Figure 2a and the Nyquist plots for all the other electrolytes were found to be in the 6−15 nF/cm 2 range and thus also consistent with impedance at the grain boundaries within each pellet.…”

Section: ■ Results and Discussionsupporting

confidence: 57%

“…In such future applications, careful attention must be paid to the membrane’s flexural strength, in addition to the evolution of its microstructure and resistance while in contact with the electrolyte. Although certain bulk mechanical properties of NaSICON have been previously measured, − the flexural strength of thin NaSICON membranes is unknown. Low flexural strength may result in fracture of the membrane while under stresses from compression against other cell components or pressure gradients caused by uneven electrolyte flow.…”

Section: Resultsmentioning

confidence: 99%

“…Von Alpen type NaSICON (Na 3.1 Zr 1.55 Si 2.3 P 0.7 O 11 ) powders were synthesized from reagent grade Na 3 PO 4 ·12H 2 O, Na 2 CO 3 , ZrO 2 , and SiO 2 precursors via calcination at 1100 °C for 10 h using the process outlined for S900C samples in ref. . NaSICON pellets were synthesized via a rapid induction hot pressing technique at 1200 °C for 40 min under flowing argon at a pressure of 47 MPa.…”

Section: Methodsmentioning

confidence: 99%

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Correlating Stability and Performance of NaSICON Membranes for Aqueous Redox Flow Batteries

Modak

Valle

Tseng

et al. 2022

ACS Appl. Mater. Interfaces

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Aqueous redox flow batteries (RFBs) are promising candidates for low-cost, grid-scale energy storage. However, the polymer-based membranes that are used in most prototypical systems fail to prevent crossover of small-molecule reactants, which results in high rates of capacity fade. In this work, we explore the feasibility of a von Alpen sodium superionic conductor Na3.1Zr1.55Si2.3P0.7O11 (NaSICON) as an RFB membrane by examining its resistance, permeability, and interfacial morphology as a function of electrolyte composition and temperature. The resistance of NaSICON is stable for several weeks while immersed in neutral to strongly alkaline ([OH–] = 3 M) aqueous electrolytes, and its permeability to polysulfide-based and permanganate-based small-molecule RFB reactants is negligible compared to that of Nafion. The glassy phase of the NaSICON microstructure at the membrane–electrolyte interface is susceptible to some etching while in contact with aqueous electrolytes containing sodium ions. This etching becomes more extensive when potassium ions are present in the electrolyte, leading in certain instances to complete disintegration of the membrane. A ∼0.7 mm-thin NaSICON membrane can nevertheless support over three weeks of cycling of a ferrocyanide|permanganate flow cell in a strongly alkaline electrolyte ([OH–] = 3 M), with apparently negligible reactant crossover and very low capacity fade (<0.04%/day). NaSICON’s area-specific resistance also decreases dramatically with increasing temperature and decreasing membrane thickness; there is a 5.6× reduction from a 1.19 mm-thick membrane at 18 °C (101 Ωcm2) to a 0.61 mm-thick one at 70 °C (18 Ωcm2). Lowering the thickness of the membrane to 0.1 mm or lower will result in power densities at above ambient temperatures that are comparable to power densities of polymer membrane-containing flow cells. This work highlights the promise of ceramic membranes as effective separators in RFBs operating under neutral pH to strongly alkaline pH conditions.

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Section: Resultssupporting

confidence: 82%

Section: ■ Results and Discussionsupporting

confidence: 57%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Correlating Stability and Performance of NaSICON Membranes for Aqueous Redox Flow Batteries

Modak

Valle

Tseng

et al. 2022

ACS Appl. Mater. Interfaces

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“…NASICON is synthesised by two main routes: solid‐state reaction and sol‐gel synthesis. [87] There are numerous manufacturing processes that affect the outcome of the solid state reaction, which are related to the size and break‐up of the particles, subsequent mixing and the formation of pellets which can be sintered, where time and temperature will differ dependent on article size and pellet geometry. [88]…”

Section: Combining and Mixingmentioning

confidence: 99%

Process‐Structure‐Formulation Interactions for Enhanced Sodium Ion Battery Development: A Review

Sawhney

Wahid²,

Griffin

et al. 2022

ChemPhysChem

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Before the viability of a cell formulation can be assessed for implementation in commercial sodium ion batteries, processes applied in cell production should be validated and optimized. This review summarizes the steps performed in constructing sodium ion (Na‐ion) cells at research scale, highlighting parameters and techniques that are likely to impact measured cycling performance. Consistent process‐structure‐performance links have been established for typical lithium‐ion (Li‐ion) cells, which can guide hypotheses to test in Na‐ion cells. Liquid electrolyte viscosity, sequence of mixing electrode slurries, rate of drying electrodes and cycling characteristics of formation were found critical to the reported capacity of laboratory cells. Based on the observed importance of processing to battery performance outcomes, the current focus on novel materials in Na‐ion research should be balanced with deeper investigation into mechanistic changes of cell components during and after production, to better inform future designs of these promising batteries.

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Inorganic Sodium Solid Electrolytes: Structure Design, Interface Engineering and Application

Liu,

Yang,

et al. 2024

Advanced Materials

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All‐solid‐state sodium batteries are particularly attractive for large‐scale energy storage and electric vehicles due to their exceptional safety, abundant resource availability, and cost‐effectiveness. The growing demand for all‐solid‐state sodium batteries underscores the significance of sodium solid electrolytes. However, the existed challenges of sodium solid electrolytes hinder their practical application despite continuous research efforts. Herein, we review recent advancements and the challenges for sodium solid electrolytes from material to battery level. The in‐depth understanding of their fundamental properties, synthesis techniques, crystal structures and recent breakthroughs are presented. Moreover, critical challenges on inorganic sodium solid electrolytes are emphasized, including the imperative need to enhance ionic conductivity, fortifying interfacial compatibility with anode/cathode materials, and addressing dendrite formation issues. Finally, potential applications of these inorganic sodium solid electrolytes are explored in all‐solid‐state sodium batteries and emerging battery systems, offering insights into future research directions.This article is protected by copyright. All rights reserved

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Characterization of hot-pressed von Alpen type NASICON ceramic electrolytes

Cited by 18 publications

References 55 publications

Correlating Stability and Performance of NaSICON Membranes for Aqueous Redox Flow Batteries

Correlating Stability and Performance of NaSICON Membranes for Aqueous Redox Flow Batteries

Process‐Structure‐Formulation Interactions for Enhanced Sodium Ion Battery Development: A Review

Inorganic Sodium Solid Electrolytes: Structure Design, Interface Engineering and Application

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