Systematic study of Co-free LiNi0.9Mn0.07Al0.03O2 Ni-rich cathode materials to realize high-energy density Li-ion batteries

Manojkumar Seenivasan; Chun-Chen Yang; She-Huang Wu; Jeng-Kuei Chang; Rajan Jose

doi:10.1016/j.jcis.2024.02.040

Systematic study of Co-free LiNi_0.9Mn_0.07Al_0.03O₂ Ni-rich cathode materials to realize high-energy density Li-ion batteries

J Colloid Interface Sci. 2024 May:661:1070-1081. doi: 10.1016/j.jcis.2024.02.040. Epub 2024 Feb 8.

Authors

Manojkumar Seenivasan¹, Chun-Chen Yang², She-Huang Wu³, Jeng-Kuei Chang⁴, Rajan Jose⁵

Affiliations

¹ Battery Research Center of Green Energy, Ming Chi University of Technology, New Taipei City 24301, Taiwan, ROC.
² Battery Research Center of Green Energy, Ming Chi University of Technology, New Taipei City 24301, Taiwan, ROC; Department of Chemical Engineering, Ming Chi University of Technology, New Taipei City 24301, Taiwan, ROC; Department of Chemical and Materials Engineering & Center for Sustainability and Energy Technologies, Chang Gung University, Taoyuan City 333, Taiwan. Electronic address: ccyang@mail.mcut.edu.tw.
³ Battery Research Center of Green Energy, Ming Chi University of Technology, New Taipei City 24301, Taiwan, ROC; Graduate Institute of Science and Technology, National Taiwan University of Science and Technology, 43, Sec. 4, Keelung Road, Taipei 106, Taiwan, ROC.
⁴ Department of Materials Science and Engineering, National Yang-Ming Chiao Tung University, 1001 University Road, Hsinchu, 30010, Taiwan, ROC.
⁵ Nanostructured Renewable Energy Materials Laboratory, Faculty of Industrial Sciences and Technology, University Malaysia Pahang, 26300 Kuantan, Malaysia.

PMID: 38368230
DOI: 10.1016/j.jcis.2024.02.040

Abstract

The growing use of EVs and society's energy needs require safe, affordable, durable, and eco-friendly high-energy lithium-ion batteries (LIBs). To this end, we synthesized and investigated the removal of Co from Al-doped Ni-rich cathode materials, specifically LiNi_0.9Co_0.1Al_0.0O₂ (NCA-0), LiNi_0.9Mn_0.1Al_0.0O₂ (NMA-0), LiNi_0.9Mn_0.07Al_0.03O₂ (NMA-3), intending to enhance LIB performance and reduce the reliance on cobalt, a costly and scarce resource. Our study primarily focuses on how the removal of Co affects the material characteristics of Ni-rich cathode material and further introduces aluminum into the cathode composition to study its impacts on electrochemical properties and overall performance. Among the synthesized samples, we discovered that the NMA-3 sample, modified with 3 mol% of Al, exhibited superior battery performance, demonstrating the effectiveness of aluminum in promoting cathode stability. Furthermore, the Al-modified cathode showed promising cycle life under normal and high-temperature conditions. Our NMA-3 demonstrated remarkable capacity retention of ∼ 88 % at 25 °C and ∼ 81 % at 45 °C after 200 cycles at 1C, within a voltage range of 2.8-4.3 V, closely matching the performances of conventional NCM and NCA cathodes. Without cobalt, the cathodes exhibited increased cation disorder leading to inferior rate capabilities at high C-rates. In-situ transmission XRD analysis revealed that the introduction of Al has reduced the phase change and provided much-needed stability to the overall structure of the Co-free NMA-3. Altogether, the findings suggest that our aluminum-modified NMA-3 sample offers a promising approach to developing Co-free, Ni-rich cathodes, effectively paving the way toward sustainable, high-energy-density LIBs.

Keywords: Cobalt-free cathodes; High-C rates; In-situ XRD; LIBs; Ni-rich cathodes.