Core-shell structure of LiMn2O4 cathode material reduces phase transition and Mn dissolution in Li-ion batteries

• Published in: Communications chemistry 2022-04, Vol.5 (1), p.1-12, Article 54
• Main Authors: Tomon, Chanikarn, Sarawutanukul, Sangchai, Phattharasupakun, Nutthaphon, Duangdangchote, Salatan, Chomkhuntod, Praeploy, Joraleechanchai, Nattanon, Bunyanidhi, Panyawee, Sawangphruk, Montree
• Format: Article
• Language: English
• Subjects: 639/4077/4079/891; 639/638/161/891; Carbon; Cathodes; Cathodic dissolution; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Core-shell structure; Cycles; Dissolution; Electric potential; Electrode materials; Fading; Lithium; Lithium manganese oxides; Lithium-ion batteries; Manganese dioxide; Oxide coatings; Phase transitions; Rechargeable batteries; Thermal stability; Toxicity; Transition metals; Voltage
• ISSN: 2399-3669; 2399-3669
• DOI: 10.1038/s42004-022-00670-y

Although the LiMn 2 O 4 cathode can provide high nominal cell voltage, high thermal stability, low toxicity, and good safety in Li-ion batteries, it still suffers from capacity fading caused by the combination of structural transformation and transition metal dissolution. Herein, a carbon-coated LiMn 2 O 4 cathode with core@shell structure (LMO@C) was therefore produced using a mechanofusion method. The LMO@C exhibits higher cycling stability as compared to the pristine LiMn 2 O 4 (P-LMO) due to its high conductivity reducing impedance growth and phase transition. The carbon shell can reduce direct contact between the electrolyte and the cathode reducing side reactions and Mn dissolution. Thus, the cylindrical cell of LMO@C//graphite provides higher capacity retention after 900 cycles at 1 C. The amount of dissoluted Mn for the LMO@C is almost 2 times lower than that of the P-LMO after 200 cycles. Moreover, the LMO@C shows smaller change in lattice parameter or phase transition than P-LMO, indicating to the suppression of λ-MnO 2 phase from the mixed phase of Li 1-δ Mn 2 O 4  + λ-MnO 2 when Li-delithiation at highly charged state leading to an improved cycling reversibility. This work provides both fundamental understanding and manufacturing scale demonstration for practical 18650 Li-ion batteries. Its high nominal voltage, thermal stability, and low toxicity render LiMn 2 O 4 a highly promising cathode material for lithium ion batteries, but capacity fading due to unwanted side reactions during cycling remains an issue. Here, the authors show that carbon-coating a LiMn 2 O 4 cathode reduces side reactions such as manganese dissolution and manganese oxide formation, thereby improving battery cycling stability.