A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

He, Yubin; Wang, Chunyang; Lin, Ruoqian; Hu, Enyuan; Trask, Stephen E.; Li, Ju; Xin, Huolin L.

doi:10.1002/adma.202406315

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

Journal Article · Thu Oct 10 00:00:00 EDT 2024 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202406315· OSTI ID:2473069

He, Yubin ^[1]; Wang, Chunyang ^[1]; Lin, Ruoqian ^[2]; ^[3]; Trask, Stephen E. ^[4]; Li, Ju ^[5]; ^[1]

University of California, Irvine, CA (United States)
University of California, Riverside, CA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Massachusetts Institute of Technology, Cambridge, MA (United States)

In this article, lithium metal (Li⁰) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode–electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h^-1. A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li⁰ stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li⁰ deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li⁺ diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li⁰–Li⁰ cells, reaching 12 000 h at 0.2 mA cm^-2 and 5000 h at 0.5 mA cm^-2. Furthermore, owing to its high critical current density of 9 mA cm^-2, the Li⁰–LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) full cell demonstrates stable cycling at 5 mA cm^-2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); DARPA MINT program

Grant/Contract Number:: SC0012704; SC0021204

OSTI ID:: 2473069

Report Number(s):: BNL--226278-2024-JAAM; GRP-COEE--38

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 49 Vol. 36; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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