Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route
Abstract
Layered oxide LiNixMnyCozO2 (NMC) cathodes are often synthesized as polycrystalline secondary particles. Due to intergranular fracture stemming from volume changes of randomly oriented primary particles during charge/discharge, the synthesis of larger single-crystalline cathodes is of high interest. In this work, molten salt assisted growth of micron-sized Ni-rich crystals is achieved with excellent crystallinity, low cation mixing, and negligible impurities. However, electrochemical performance is compromised by high surface reactivity resulting in decomposition of electrolyte and subsequent formation of a thick CEI layer. While intergranular fracture is eliminated, planar gliding and severe intragranular fracture along the (003) plane occurs in the high voltage region within the first few cycles and is associated primarily with H2 to H3 structural transitions. In addition, H2 to H3 transitions are highly irreversible with cyclic voltammograms revealing polarization growth within <5 cycles. Subsequently, the single-crystalline material exhibited markedly reduced available capacity and enhanced capacity fade from sharp impedance growth compared to its polycrystalline counterpart. Here, this work furthers a fundamental understanding into the limitations of single-crystalline Ni-rich cathodes, and the obstacles limiting the advantages offered by the single-crystalline morphology.
- Authors:
-
[1];
[1];
[1]
- Worcester Polytechnic Institute, MA (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Rice Univ., Houston, TX (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); Ford Motor Company
- OSTI Identifier:
- 1902347
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Power Sources
- Additional Journal Information:
- Journal Volume: 545; Journal ID: ISSN 0378-7753
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Li-ion battery; LiNi0.8Mn0.1Co0.1O; NMC; Single-crystal; intragranular fracture
Citation Formats
Azhari, Luqman, Meng, Zifei, Yang, Zhenzhen, Gao, Guanhui, Han, Yimo, and Wang, Yan. Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route. United States: N. p., 2022.
Web. doi:10.1016/j.jpowsour.2022.231963.
Azhari, Luqman, Meng, Zifei, Yang, Zhenzhen, Gao, Guanhui, Han, Yimo, & Wang, Yan. Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route. United States. https://doi.org/10.1016/j.jpowsour.2022.231963
Azhari, Luqman, Meng, Zifei, Yang, Zhenzhen, Gao, Guanhui, Han, Yimo, and Wang, Yan. Wed .
"Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route". United States. https://doi.org/10.1016/j.jpowsour.2022.231963. https://www.osti.gov/servlets/purl/1902347.
@article{osti_1902347,
title = {Underlying limitations behind impedance rise and capacity fade of single crystalline Ni-rich cathodes synthesized via a molten-salt route},
author = {Azhari, Luqman and Meng, Zifei and Yang, Zhenzhen and Gao, Guanhui and Han, Yimo and Wang, Yan},
abstractNote = {Layered oxide LiNixMnyCozO2 (NMC) cathodes are often synthesized as polycrystalline secondary particles. Due to intergranular fracture stemming from volume changes of randomly oriented primary particles during charge/discharge, the synthesis of larger single-crystalline cathodes is of high interest. In this work, molten salt assisted growth of micron-sized Ni-rich crystals is achieved with excellent crystallinity, low cation mixing, and negligible impurities. However, electrochemical performance is compromised by high surface reactivity resulting in decomposition of electrolyte and subsequent formation of a thick CEI layer. While intergranular fracture is eliminated, planar gliding and severe intragranular fracture along the (003) plane occurs in the high voltage region within the first few cycles and is associated primarily with H2 to H3 structural transitions. In addition, H2 to H3 transitions are highly irreversible with cyclic voltammograms revealing polarization growth within <5 cycles. Subsequently, the single-crystalline material exhibited markedly reduced available capacity and enhanced capacity fade from sharp impedance growth compared to its polycrystalline counterpart. Here, this work furthers a fundamental understanding into the limitations of single-crystalline Ni-rich cathodes, and the obstacles limiting the advantages offered by the single-crystalline morphology.},
doi = {10.1016/j.jpowsour.2022.231963},
journal = {Journal of Power Sources},
number = ,
volume = 545,
place = {United States},
year = {Wed Aug 17 00:00:00 EDT 2022},
month = {Wed Aug 17 00:00:00 EDT 2022}
}
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