Machinable, high‐conductivity NaSICON through mitigation of humidity effects during solid‐state synthesis

Peretti, Amanda Sheree; Spoerke, Erik David; Ureña, Michael Earl; Dyer, Isaac D.; Salinas, Perla Arely; Rodriguez, Mark. Andrew; Mantos, Philip Stewart; Williard, John Newsom; Small, Leo Joseph

doi:10.1111/jace.70195

Machinable, high‐conductivity NaSICON through mitigation of humidity effects during solid‐state synthesis

Journal Article · Thu Sep 04 00:00:00 EDT 2025 · Journal of the American Ceramic Society

DOI:https://doi.org/10.1111/jace.70195· OSTI ID:2588302

^[1]; ^[1]; ^[1]; ^[1]; Salinas, Perla Arely ^[1]; ^[1]; Mantos, Philip Stewart ^[1]; Williard, John Newsom ^[1]; ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

The Na⁺ super ion conductor (NaSICON, Na_1+xZr₂Si_xP_3-xO₁₂) is a solid electrolyte well-known for fast, selective Na⁺ transport at low temperatures, uniquely enabling sodium-based batteries. Producing high-quality NaSICON from solid-state methods, especially when cost-effective, potentially hygroscopic precursors are used, is not trivial. To understand and eliminate the influence of humidity during processing, a scheme was developed to reproducibly yield a high Na⁺ conductivity (3.75 mS/cm at 25°C, 81.7 mS/cm at 150°C), high density (97%), and machinable NaSICON without the use of binders, sintering aids, or dopants. Controlled humidity studies over 20%–50% RH coupled with thermal, structural, and electrical analysis reveal that calcination temperatures < 1000°C leave NaSICON processing susceptible to water absorption at > 20% RH due to the presence of hygroscopic Na₃PO₄ and Na₂CO₃ during shaping, pressing, and sintering. Water absorption results in NaSICON with lower densities, machinability, and Na+ conductivity, due to impaired intergranular Na+ transport. At the other extreme, fully converting precursor to the NaSICON phase at 1230°C before pressing and sintering leads to poor conductivity and density. By calcining at 1000°C, excellent quality NaSICON may be produced under a range of laboratory environments, enabling low-cost production of high-conductivity, machinable NaSICON necessary the ever-growing energy storage market.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Electricity (OE)

Grant/Contract Number:: NA0003525

OSTI ID:: 2588302

Report Number(s):: SAND--2025-11432J; 1771370

Journal Information:: Journal of the American Ceramic Society, Journal Name: Journal of the American Ceramic Society Journal Issue: 12 Vol. 108; ISSN 0002-7820; ISSN 1551-2916

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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ceramic
humidity
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Machinable, high‐conductivity NaSICON through mitigation of humidity effects during solid‐state synthesis

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