Abstract
Sulfide solid-state electrolytes (SSEs) in all-solid-state batteries (SSBs) are recognized for their high ionic conductivity and inherent safety. The LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode offers a high thermodynamic potential of approximately 3.8 V vs. Li/Li+ and a theoretical specific capacity of 200 mA h g−1. However, the practical utilization of NMC811 in sulfide SSBs faces significant interfacial challenges. The oxidation instability of sulfide solid electrolytes against NMC811 and the formation of the cathode electrolyte interphase (CEI) during cycling lead to degradation and reduced cell performance. Volumetric changes in NMC during lithiation and de-lithiation can also cause detachment from sulfide electrolytes or internal particle cracking. Despite extensive galvanostatic cycling studies to address the issues, the calendar life of sulfide SSBs remains poorly understood. Here, we systematically studied the effects of four different catholytes on the calendar aging of LiNbO3 (LNO)-coated NMC811, including Li6PS5Cl (LPSCl), Li3InCl6-Li6PS5Cl (LIC-LPSCl), Li3YCl6-Li6PS5Cl (LYC-LPSCl), and Li10GeP2S12 (LGPS). Our results indicate that LPSCl provides optimal capacity retention when stored at high state-of-charge (SOC) at room temperature, but the LIC-LPSCl cathode shows significant capacity degradation and chemical incompatibility. We also established an effective electrochemical calendar aging testing protocol to simulate daily usage, enabling quick inference of the calendar life of SSBs. This new testing approach accelerates materials selection strategies for high-nickel NMC composite cathodes in sulfide SSBs.
| Original language | English |
|---|---|
| Pages (from-to) | 119-130 |
| Number of pages | 12 |
| Journal | Materials Horizons |
| Volume | 12 |
| Issue number | 1 |
| DOIs | |
| State | Published - Oct 25 2024 |
Funding
This research was conducted at the Oak Ridge National Laboratory, managed by UT Battelle, LLC for the U.S. Department of Energy (DOE) and is sponsored by the Office of Energy Efficiency and Renewable Energy (EERE) in the Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program, managed by Drs Simon Thompson and Tien Duong. This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. SEM and EDX research were conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. XPS was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-2026822. The use of the Stanford Synchrotron Radiation Lightsource at SLAC National Accelerator Laboratory is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. Y. C. was supported by the Japan Society for the Promotion of Science (JSPS) overseas research fellowship and the Stanford Energy Postdoctoral Fellowship and the Precourt Institute for Energy.