skip to main content

Title: Effect of the grain arrangements on the thermal stability of polycrystalline nickel-rich lithium-based battery cathodes

One of the most challenging aspects of developing high-energy lithium-based batteries is the structural and (electro)chemical stability of Ni-rich active cathode materials at thermally-abused and prolonged cell cycling conditions. Here, we report in situ physicochemical characterizations to improve the fundamental understanding of the degradation mechanism of charged polycrystalline Ni-rich cathodes at elevated temperatures (e.g., ≥ 40 °C). Using multiple microscopy, scattering, thermal, and electrochemical probes, we decouple the major contributors for the thermal instability from intertwined factors. Our research work demonstrates that the grain microstructures play an essential role in the thermal stability of polycrystalline lithium-based positive battery electrodes. We also show that the oxygen release, a crucial process during battery thermal runaway, can be regulated by engineering grain arrangements. Furthermore, the grain arrangements can also modulate the macroscopic crystallographic transformation pattern and oxygen diffusion length in layered oxide cathode materials.

more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Nature Communications
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. The driving mileage of electric vehicles (EVs) has been substantially improved in recent years with the adoption of Ni-based layered oxide materials as the battery cathode. The average charging period of EVs is still time-consuming, compared with the short refueling time of an internal combustion engine vehicle. With the guidance from the United States Department of Energy, the charging time of refilling 60% of the battery capacity should be less than 6 min for EVs, indicating that the corresponding charging rate for the cathode materials is to be greater than 6C. However, the sluggish kinetic conditions and insufficient thermal stability of the Ni-based layered oxide materials hinder further application in fast-charging operations. Most of the recent review articles regarding Ni-based layered oxide materials as cathodes for lithium-ion batteries (LIBs) only touch degradation mechanisms under slow charging conditions. Of note, the fading mechanisms of the cathode materials for fast-charging, of which the importance abruptly increases due to the development of electric vehicles, may be significantly different from those of slow charging conditions. There are a few review articles regarding fast-charging; however, their perspectives are limited mostly to battery thermal management simulations, lacking experimental validations such as microscale structure degradations of Ni-based layered oxide cathode materials. In this review, a general and fundamental definition of fast-charging is discussed at first, and then we summarize the rate capability required in EVs and the electrochemical and kinetic properties of Ni-based layered oxide cathode materials. Next, the degradation mechanisms of LIBs leveraging Ni-based cathodes under fast-charging operation are systematically discussed from the electrode scale to the particle scale and finally the atom scale (lattice oxygen-level investigation). Then, various strategies to achieve higher rate capability, such as optimizing the synthesis process of cathode particles, fabricating single-crystalline particles, employing electrolyte additives, doping foreign ions, coating protective layers, and engineering the cathode architecture, are detailed. All these strategies need to be considered to enhance the electrochemical performance of Ni-based oxide cathode materials under fast-charging conditions. 
    more » « less
  2. Efficient heat dissipation in batteries is important for thermal management against thermal runaway and chemical instability at elevated temperatures. Nevertheless, thermal transport processes in battery materials have not been well understood especially considering their complicated microstructures. In this study, lattice thermal transport in lithium cobalt oxide (LiCoO 2 ), a popular cathode material for lithium ion batteries, is investigated via molecular dynamics-based approaches and thermal resistance models. A LiCoO 2 single-crystal is shown to have thermal conductivities in the order of 100 W m −1 K −1 with strong anisotropy, temperature dependence, and size effects. By comparison, polycrystalline LiCoO 2 is more isotropic with much lower thermal conductivities. This difference is caused by random grain orientations, the thermal resistance of grain boundaries, and size-dependent intra-grain thermal conductivities that are unique to polycrystals. The grain boundary thermal conductance is calculated to be in the range of 7.16–25.21 GW m −2 K −1 . The size effects of the intra-grain thermal conductivities are described by two empirical equations. Considering all of these effects, two thermal resistance models are developed to predict the thermal conductivity of polycrystalline LiCoO 2 . The two models predict a consistent thermal conductivity–grain size relationship that agrees well with molecular dynamics simulation results. The insights revealed by this study may facilitate future efforts on battery materials design for improved thermal management. 
    more » « less
  3. Abstract

    Architecting grain crystallographic orientation can modulate charge distribution and chemomechanical properties for enhancing the performance of polycrystalline battery materials. However, probing the interplay between charge distribution, grain crystallographic orientation, and performance remains a daunting challenge. Herein, we elucidate the spatially resolved charge distribution in lithium layered oxides with different grain crystallographic arrangements and establish a model to quantify their charge distributions. While the holistic “surface-to-bulk” charge distribution prevails in polycrystalline particles, the crystallographic orientation-guided redox reaction governs the charge distribution in the local charged nanodomains. Compared to the randomly oriented grains, the radially aligned grains exhibit a lower cell polarization and higher capacity retention upon battery cycling. The radially aligned grains create less tortuous lithium ion pathways, thus improving the charge homogeneity as statistically quantified from over 20 million nanodomains in polycrystalline particles. This study provides an improved understanding of the charge distribution and chemomechanical properties of polycrystalline battery materials.

    more » « less
  4. Cost-effective production of low cobalt Li-ion battery (LIB) cathode materials is of great importance to the electric vehicle (EV) industry to achieve a zero-carbon economy. Among the various low cobalt cathodes, Ni-rich lithium nickel cobalt manganese oxide (NCM/NMC)-based layered materials are commonly used in EVs and are attracting more attention of the scientific community due to their high specific capacity and energy density. Various synthesis routes are already established to produce Ni-rich NCM cathodes with uniform particle size distribution and high tap density. Continuous production of highly pure Ni-rich cathode materials with uniformity in inter/intra-particle compositional distribution is critically required. On the other hand, cation mixing, particle cracking, and parasitic side reactions at higher voltage and temperature are some of the primary challenges of working with Ni-rich NCM cathodes. During the past five years, several advanced modification strategies such as coating, doping, core–shell, gradient structure and single crystal growth have been explored to improve the NCM cathode performance in terms of specific capacity, rate-capability and cycling stability. The scientific advancements in the field of Ni-rich NCM cathodes in terms of manufacturing processes, material challenges, modification techniques, and also the future research direction of LIB research are critically reviewed in this article. 
    more » « less
  5. Abstract

    With the rapid growth of the lithium‐ion battery (LIBs) market, recycling and re‐use of end‐of‐life LIBs to reclaim lithium (Li) and transition metal (TM) resources (e.g., Co, Ni), as well as eliminating pollution from disposal of waste batteries, has become an urgent task. Here, for the first time the ambient‐pressure relithiation of degraded LiNi0.5Co0.2Mn0.3O2(NCM523) cathodes via eutectic Li+molten‐salt solutions is successfully demonstrated. Combining such a low‐temperature relithiation process with a well‐designed thermal annealing step, NCM523 cathode particles with significant Li loss (≈40%) and capacity degradation (≈50%) can be successfully regenerated to achieve their original composition and crystal structures, leading to effective recovery of their capacity, cycling stability, and rate capability to the levels of the pristine materials. Advanced characterization tools including atomic resolution electron microscopy imaging and electron energy loss spectroscopy are combined to demonstrate that NCM523's original layered crystal structure is recovered. For the first time, it is shown that layer‐to‐rock salt phase change on the surfaces and subsurfaces of the cathode materials can be reversed if lithium can be incorporated back to the material. The result suggests the great promise of using eutectic Li+molten–salt solutions for ambient‐pressure relithiation to recycle and remanufacture degraded LIB cathode materials.

    more » « less