skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Design principles for sodium superionic conductors
Abstract Motivated by the high-performance solid-state lithium batteries enabled by lithium superionic conductors, sodium superionic conductor materials have great potential to empower sodium batteries with high energy, low cost, and sustainability. A critical challenge lies in designing and discovering sodium superionic conductors with high ionic conductivities to enable the development of solid-state sodium batteries. Here, by studying the structures and diffusion mechanisms of Li-ion versus Na-ion conducting solids, we reveal the structural feature of face-sharing high-coordination sites for fast sodium-ion conductors. By applying this feature as a design principle, we discover a number of Na-ion conductors in oxides, sulfides, and halides. Notably, we discover a chloride-based family of Na-ion conductors NaxMyCl6(M = La–Sm) with UCl3-type structure and experimentally validate with the highest reported ionic conductivity. Our findings not only pave the way for the future development of sodium-ion conductors for sodium batteries, but also consolidate design principles of fast ion-conducting materials for a variety of energy applications.  more » « less
Award ID(s):
2118838
PAR ID:
10540970
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Publisher / Repository:
Nature Communications
Date Published:
Journal Name:
Nature Communications
Volume:
14
ISSN:
2041-1723
Page Range / eLocation ID:
7615
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, Small)
    Abstract Over the past decade, solid‐state batteries have garnered significant attentions due to their potentials to deliver high energy density and excellent safety. Considering the abundant sodium (Na) resources in contrast to lithium (Li), the development of sodium‐based batteries has become increasingly appealing. Sulfide‐based superionic conductors are widely considered as promising solid eletcrolytes (SEs) in solid‐state Na batteries due to the features of high ionic conductivity and cold‐press densification. In recent years, tremendous efforts have been made to investigate sulfide‐based Na‐ion conductors on their synthesis, compositions, conductivity, and the feasibility in batteries. However, there are still several challenges to overcome for their practical applications in high performance solid‐state Na batteries. This article provides a comprehensive update on the synthesis, structure, and properties of three dominant sulfide‐based Na‐ion conductors (Na3PS4, Na3SbS4, and Na11Sn2PS12), and their families that have a variety of anion and cation doping. Additionally, the interface stability of these sulfide electrolytes toward the anode is reviewed, as well as the electrochemical performance of solid‐state Na batteries based on different types of cathode materials (metal sulfides, oxides, and organics). Finally, the perspective and outlook for the development and practical utilization of sulfide‐based SE in solid‐state batteries are discussed. 
    more » « less
  2. ; ; ; ; (, ChemRxiv)
    The layered transition metal chalcogenides MCrX2 (M = Ag, Cu; X = S, Se, Te) are of interest for energy storage because chemically Li-substituted analogs were reported as superionic Li+ conductors. The coexistence of fast ion transport and reducible transition metal and chalcogen elements suggests that this family may offer multifunctional capability for electrochemical storage. Here, we investigate the electrochemical reduction of AgCrSe2 and CuCrSe2 in non-aqueous Li- and Na-ion electrolytes using electrochemical measurements coupled with ex situ characterization (scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy). Both compounds delivered high initial specific capacities (~ 560 mAh/g), corresponding to 6.64 and 5.73 Li+/e- per formula unit for AgCrSe2 and CuCrSe2, respectively. We attribute this difference to distinct reduction pathways: 1) Li+ intercalation to form LiCrSe2 and extruded Ag or Cu, 2) conversion of LiCrSe2 to Li2Se, and 3) formation of an Ag-Li alloy at the lowest potential, operative only in AgCrSe2. Consistent with this proposed mechanism, step 3 was absent during reduction of AgCrSe2 in a Na-ion electrolyte since Ag does not alloy with Na. These results demonstrate the complex reduction chemistry of MCrX2 in the presence of alkali ions, providing insights into the use of MCrX2 materials as alkali ion superionic conductors or high capacity electrodes for lithium or sodium-ion type batteries. 
    more » « less
  3. ; ; ; ; ; ; ; (, Small)
    Abstract Rechargeable solid‐state sodium metal batteries (SSMBs) experience growing attention owing to the increased energy density (vs Na‐ion batteries) and cost‐effective materials. Inorganic sulfide‐based Na‐ion conductors also possess significant potential as promising solid electrolytes (SEs) in SSMBs. Nevertheless, due to the highly reactive Na metal, poor interface compatibility is the biggest obstacle for inorganic sulfide solid electrolytes such as Na3SbS4to achieve high performance in SSMBs. To address such electrochemical instability at the interface, new design of sulfide SE nanostructures and interface engineering are highly essential. In this work, a facile and straightforward approach is reported to prepare 3D sulfide‐based solid composite electrolytes (SCEs), which utilize porous Na3SbS4(NSS) as a self‐templated framework and fill with a phase transition polymer. The 3D structured SCEs display obviously improved interface stability toward Na metal than pristine sulfide. The assembled SSMBs (with TiS2or FeS2as cathodes) deliver outstanding electrochemical cycling performance. Moreover, the cycling of high‐voltage oxide cathode Na0.67Ni0.33Mn0.67O2(NNMO) is also demonstrated in SSMBs using 3D sulfide‐based SCEs. This study presents a novel design on the self‐templated nanostructure of SCEs, paving the way for the advancement of high‐energy sodium metal batteries. 
    more » « less
  4. ; ; ; ; ; ; ; ; ; ; et al (, Science)
    Solid-state batteries are attractive energy storage systems as a result of their inherent safety, but their development hinges on advanced solid-state electrolytes (SSEs). Most SSEs remain largely confined to single-anion systems (e.g., sulfides, oxides, halides, and polymers). Through mixed-anion design strategy, we develop crystalline Li3Ta3O4Cl10(LTOC) and its derivatives with excellent ionic conductivities (up to 13.7 millisiemens per centimeter at 25°C) and electrochemical stability. The LTOC structure features mixed-anion spiral chains, consisting of corner-shared oxygen and terminal chlorine atoms, which induces continuous “tetrahedron-tetrahedron” Li-ion migration pathways with low energy barriers. Additionally, LTOC demonstrates holistic cathode compatibility, enabling solid-state batteries operation at 4.9 volts versus Li/Li+and low temperature, down to −50°C. These findings describe a promising class of superionic conductors for high-performance solid-state batteries. 
    more » « less
  5. ; ; ; (, Journal of The Electrochemical Society)
    Abstract Intermittent renewable energy sources can mitigate climate change, but they require high-performance, reliable batteries. The widely used lithium-ion batteries contain Li, Co, and Ni, and the growing demand for these elements, together with their relatively limited sources, has raised concerns about their supply chain stability. Sodium-ion batteries have become an economical alternative. Sodium vanadium phosphate, Na3V2(PO4)3 (NVP), is a compelling candidate with high stability and ionic conductivity due to its polyanionic sodium superionic conductor (NASICON) structure. However, NVP suffers from poor electronic conductivity and requires hierarchical morphology to allow facile ion and electron transfer. Spray-drying has been used to achieve hierarchical secondary particle structures, but the foremost reported NVP syntheses rely on either flammable/toxic organic solvents or expensive nanocarbon additives. In this study, we spray-dry an aqueous suspension without using expensive carbon additives. The obtained NVP sodium-ion half cells showed very high reversible capacity (114.7 mAh g-1 at 0.2C), high rate capability (80.8% capacity retention at 30C), and stable cycling performance (96.7% capacity retention after 1,500 cycles at 10C). This superior performance demonstrates the great promise for NVP batteries as an alternative energy storage option to traditional lithium-ion batteries. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Text Encoded Conversion
  • XML
  • Save / Share this Record
  • Send to Email