Medium-Range Ordering in the Ionic Glass Electrolytes LiPON and LiSiPON

Westover, Andrew S.; Kornbluth, Mordechai; Egami, T.; Liu, Jue; Kalnaus, Sergiy; Ma, Dong; Kercher, Andrew K.; Neuefeind, Jöerg C.; Everett, S. Michelle; Torres, Victor M.; Martin, Steve W.; Kozinsky, Boris; Dudney, Nancy J.

doi:10.1021/acs.chemmater.2c02380

Cited by 4 publications

(1 citation statement)

References 42 publications

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“…Consequently, these oxide electrolytes have found successful commercial applications in thin film batteries. Furthermore, the admirable mechanical properties of LiPON have resulted in a resurgence in the study of this material for all-solid batteries at a large scale, where the main challenge is to process the electrolyte into sufficiently thin films at a low cost. − …”

Section: Introductionmentioning

confidence: 99%

Pioneering Combinatorial Investigation to Unlock the Potential of Lithium Borosilicate Glasses as Solid Electrolytes

Jonderian,

Rehman,

Card Gormley

et al. 2024

ACS Appl. Energy Mater.

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The development of solid-state electrolytes for lithiumion batteries (LIBs) focuses on enhancing the safety, lifetime, and energy density. Lithium borosilicate glass ceramics (LBS) have garnered interest due to their electrochemical stability and deformability. However, achieving highly ionic conductive glasses requires fully glassy LBS compositions at high lithium contents and this remains a challenge. To date, only a handful of Li−B−Si−O compositions have been studied as prospective solid electrolytes. Herein, we developed the combinatorial synthesis of glasses by the melt-quench method. We adapted our highthroughput techniques to be able to obtain XRD, ionic conductivity, electronic conductivity, and the electrochemical stability window on these glasses. Furthermore, we designed a high-throughput softness measuring system with exceptional precision for effective determination of deformability and this test demonstrates excellent correlation with the glass transition temperature (a measurement that cannot be performed in high-throughput). Our investigations explored the influence of composition in over 360 different combinations of Li−B−Si−X−O where X are substituents from a list of 55 elements. Low level substitution (1%) was found to increase the solubility of Li in the glasses which in turn dramatically increased the deformability and gave a moderate improvement in ionic conductivity. In addition, our study unveiled that substitutions have an impact on the electrochemical stability window with the Zn-substituted glass demonstrating a greater anodic stability limit compared to the unsubstituted LBS electrolyte. Overall, this study provides valuable insights into lithium borosilicate composition−property relations. Extending combinatorial techniques to the study of glassy solid electrolytes opens up many avenues for accelerated design of this class of materials.

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Section: Introductionmentioning

confidence: 99%

Pioneering Combinatorial Investigation to Unlock the Potential of Lithium Borosilicate Glasses as Solid Electrolytes

Jonderian,

Rehman,

Card Gormley

et al. 2024

ACS Appl. Energy Mater.

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Lithium Phosphorous Oxynitride as an Advanced Solid‐State Electrolyte to Boost High‐Energy Lithium Metal Battery

Zou,

Xiao,

Lin

et al. 2024

Adv Funct Materials

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Lithium phosphorous oxynitride (LiPON) as one of the most successful solid‐state electrolytes (SSEs), has attracted great interest both in academia and technology due to its exceptional interfacial compatibility, broad electrochemical stability window, and excellent thermal stability, which enables the realization of extremely stable electrolyte/electrode interphase toward high‐energy density solid‐state lithium‐metal batteries (SSLMBs). However, insufficiency in ionic diffusion, mechanical robustness, and interfacial stability hinder its commercialization process. Herein, the characteristics of amorphous structure LiPON, fundamental understanding on the bulk ionic diffusion and electrode/electrolyte interface are systematically discussed, and the improvement strategies to boost the electrochemical performance are highlighted. Then, innovative characterization and computational methods help to unravel the design principle of LiPON are summarized. Furthermore, the approaches to realize high‐efficient preparation of LiPON are analyzed, followed by the investigation of present application of LiPON in current batteries. Finally, remaining challenges associated with the fundamental understanding and rational prediction of structure and interface design, high efficient preparation, and potential opportunities for future application of LiPON are properly prospected.

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High‐Throughput Experimentation Unveils Composition – Structure – Conductivity Relationships in the Extended LiPON System

Berthou,

Legallais,

Sorieul

et al. 2024

Advanced Energy Materials

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A high‐throughput experimental approach is developed to assess the correlations between chemical composition, structure and conduction properties of inorganic solid ionic conductors. This approach covers the preparation of a large number of samples by combinatorial synthesis, followed by fast characterization of the material library. The approach is primarily based on combinatorial synthesis by magnetron co‐sputtering and the characterization of thin film samples where lithium phosphorus oxynitride (LiPON) is chosen as a case study. A library of 76 LiPON materials is prepared in one experiment from the reactive co‐sputtering of LiPO3 and Li3PO4 in a N2 atmosphere. A specific sample design allows conducting thickness and impedance measurements, Raman spectroscopy, then fast and spatially‐resolved chemical analysis by Laser‐Induced Breakdown Spectroscopy (LIBS) on each material. Particular developments are devoted to this technique to achieve quantitative analysis of lithium in thin films. The materials cover a wide range of compositions with 0.95<Li/P<2.03 and a high N/P nitrogen content of ≈1.0‐1.2. Two distinct compositional ranges can be distinguished. For 0.95<Li/P<1.2, conductivity increases and the PO3− chains gradually disappear, whereas for 1.2<Li/P<2.03, conductivity stabilizes despite continuous structural evolution, in parallel with an increase in charge carrier concentration.

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Medium-Range Ordering in the Ionic Glass Electrolytes LiPON and LiSiPON

Cited by 4 publications

References 42 publications

Pioneering Combinatorial Investigation to Unlock the Potential of Lithium Borosilicate Glasses as Solid Electrolytes

Pioneering Combinatorial Investigation to Unlock the Potential of Lithium Borosilicate Glasses as Solid Electrolytes

Lithium Phosphorous Oxynitride as an Advanced Solid‐State Electrolyte to Boost High‐Energy Lithium Metal Battery

High‐Throughput Experimentation Unveils Composition – Structure – Conductivity Relationships in the Extended LiPON System

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