skip to main content


Title: High‐Voltage Charging‐Induced Strain, Heterogeneity, and Micro‐Cracks in Secondary Particles of a Nickel‐Rich Layered Cathode Material
Abstract

Nickel‐rich layered materials LiNi1‐x‐yMnxCoyO2are promising candidates for high‐energy‐density lithium‐ion battery cathodes. Unfortunately, they suffer from capacity fading upon cycling, especially with high‐voltage charging. It is critical to have a mechanistic understanding of such fade. Herein, synchrotron‐based techniques (including scattering, spectroscopy, and microcopy) and finite element analysis are utilized to understand the LiNi0.6Mn0.2Co0.2O2material from structural, chemical, morphological, and mechanical points of view. The lattice structural changes are shown to be relatively reversible during cycling, even when 4.9 V charging is applied. However, local disorder and strain are induced by high‐voltage charging. Nano‐resolution 3D transmission X‐ray microscopy data analyzed by machine learning methodology reveal that high‐voltage charging induced significant oxidation state inhomogeneities in the cycled particles. Regions at the surface have a rock salt–type structure with lower oxidation state and build up the impedance, while regions with higher oxidization state are scattered in the bulk and are likely deactivated during cycling. In addition, the development of micro‐cracks is highly dependent on the pristine state morphology and cycling conditions. Hollow particles seem to be more robust against stress‐induced cracks than the solid ones, suggesting that morphology engineering can be effective in mitigating the crack problem in these materials.

 
more » « less
Award ID(s):
1832613 1832707
NSF-PAR ID:
10461452
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
29
Issue:
18
ISSN:
1616-301X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Surface lattice reconstruction is commonly observed in nickel-rich layered oxide battery cathode materials, causing unsatisfactory high-voltage cycling performance. However, the interplay of the surface chemistry and the bulk microstructure remains largely unexplored due to the intrinsic structural complexity and the lack of integrated diagnostic tools for a thorough investigation at complementary length scales. Herein, by combining nano-resolution X-ray probes in both soft and hard X-ray regimes, we demonstrate correlative surface chemical mapping and bulk microstructure imaging over a single charged LiNi0.8Mn0.1Co0.1O2(NMC811) secondary particle. We reveal that the sub-particle regions with more micro cracks are associated with more severe surface degradation. A mechanism of mutual modulation between the surface chemistry and the bulk microstructure is formulated based on our experimental observations and finite element modeling. Such a surface-to-bulk reaction coupling effect is fundamentally important for the design of the next generation battery cathode materials.

     
    more » « less
  2. Abstract

    A new concentrated ternary salt ether‐based electrolyte enables stable cycling of lithium metal battery (LMB) cells with high‐mass‐loading (13.8 mg cm−2, 2.5 mAh cm−2) NMC622 (LiNi0.6Co0.2Mn0.2O2) cathodes and 50 μm Li anodes. Termed “CETHER‐3,” this electrolyte is based on LiTFSI, LiDFOB, and LiBF4with 5 vol% fluorinated ethylene carbonate in 1,2‐dimethoxyethane. Commercial carbonate and state‐of‐the‐art binary salt ether electrolytes were also tested as baselines. With CETHER‐3, the electrochemical performance of the full‐cell battery is among the most favorably reported in terms of high‐voltage cycling stability. For example, LiNixMnyCo1–xyO2(NMC)‐Li metal cells retain 80% capacity at 430 cycles with a 4.4 V cut‐off and 83% capacity at 100 cycles with a 4.5 V cut‐off (charge at C/5, discharge at C/2). According to simulation by density functional theory and molecular dynamics, this favorable performance is an outcome of enhanced coordination between Li+and the solvent/salt molecules. Combining advanced microscopy (high‐resolution transmission electron microscopy, scanning electron microscopy) and surface science (X‐ray photoelectron spectroscopy, time‐of‐fight secondary ion mass spectroscopy, Fourier‐transform infrared spectroscopy, Raman spectroscopy), it is demonstrated that a thinner and more stable cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) are formed. The CEI is rich in lithium sulfide (Li2SO3), while the SEI is rich in Li3N and LiF. During cycling, the CEI/SEI suppresses both the deleterious transformation of the cathode R‐3m layered near‐surface structure into disordered rock salt and the growth of lithium metal dendrites.

     
    more » « less
  3. Abstract

    Ni‐rich LiNi0.8Co0.1Mn0.1O2(NCM811) has been considered as a promising cathode material for high energy density lithium‐ion batteries. However, it experiences undesirable interfacial side‐reactions with the electrolyte, which lead to a rapid capacity decay. In this work, a homogeneous precipitation method is proposed for forming a uniform silicon dioxide (SiO2) coating on the NCM811 surface. The strong Si−O network provided a stable protective layer between the NCM811 active material and electrolyte to improve the electrochemical stability. As a result, the NCM811@SiO2cathode showed superior cycling stability (84.9 % after 100 cycles at 0.2 C) and rate capability (142.7 mA h g−1at 5 C) compared to the pristine NCM811 cathode (56.6 % after 100 cycles, 127.9 mA h g−1at 5 C). Moreover, the SiO2coating effectively suppressed voltage decay and pulverization of the NCM811 particles during long term cycling. This uniform coating technique offers a viable approach for stabilizing Ni‐rich cathode materials for high‐energy density lithium‐ion batteries.

     
    more » « less
  4. Abstract

    LiNO3is a widely used salt‐additive that markedly improves the stability of ether‐based electrolytes at a Li metal anode but is generally regarded as incompatible with alkyl carbonates. Here we find that contrary to common wisdom, cyclic carbonate solvents such as ethylene carbonate can dissolve up to 0.7 M LiNO3without any additives, largely improving the anode reversibility. We demonstrate the significance of our findings by upgrading various state‐of‐the‐art carbonate electrolytes with LiNO3, which provides large improvements in batteries composed of thin lithium (50 μm) anode and high voltage cathodes. Capacity retentions of 90.5 % after 600 cycles and 92.5 % after 200 cycles are reported for LiNi0.6Mn0.2Co0.2O2(2 mAh cm−2, 0.5 C) and LiNi0.8Mn0.1Co0.1O2cathode (4 mAh cm−2, 0.2 C), respectively. 1 Ah pouch cells (≈300 Wh kg−1) retain more than 87.9 % after 100 cycles at 0.5 C. This work illustrates that reforming traditional carbonate electrolytes provides a scalable, cost‐effective approach towards practical LMBs.

     
    more » « less
  5. Abstract

    LiNO3is a widely used salt‐additive that markedly improves the stability of ether‐based electrolytes at a Li metal anode but is generally regarded as incompatible with alkyl carbonates. Here we find that contrary to common wisdom, cyclic carbonate solvents such as ethylene carbonate can dissolve up to 0.7 M LiNO3without any additives, largely improving the anode reversibility. We demonstrate the significance of our findings by upgrading various state‐of‐the‐art carbonate electrolytes with LiNO3, which provides large improvements in batteries composed of thin lithium (50 μm) anode and high voltage cathodes. Capacity retentions of 90.5 % after 600 cycles and 92.5 % after 200 cycles are reported for LiNi0.6Mn0.2Co0.2O2(2 mAh cm−2, 0.5 C) and LiNi0.8Mn0.1Co0.1O2cathode (4 mAh cm−2, 0.2 C), respectively. 1 Ah pouch cells (≈300 Wh kg−1) retain more than 87.9 % after 100 cycles at 0.5 C. This work illustrates that reforming traditional carbonate electrolytes provides a scalable, cost‐effective approach towards practical LMBs.

     
    more » « less