TY - JOUR
T1 - Regulating Ni 3d-O 2p Orbital Interaction with Position-Isomer Organic Lithiation Additive for High-Voltage LiNi0.8Co0.1Mn0.1O2 Cathode
AU - Zhang, Xinyu
AU - Wang, Xianshu
AU - Cao, Yuanpeng
AU - Zhao, Chao
AU - Tu, Wenhui
AU - Zhao, Yun
AU - Dong, Peng
AU - Zhang, Yingjie
AU - Luo, Zhongyuan
AU - Wang, Ding
AU - Li, Baohua
AU - Guo, Zhenyu
AU - Titirici, Maria Magdalena
AU - Duan, Jianguo
N1 - Publisher Copyright:
© 2026 Wiley-VCH GmbH.
PY - 2026/4/8
Y1 - 2026/4/8
N2 - High-voltage nickel-rich layered oxide cathodes have attracted much attention due to their high capacity and elevated voltage plateau. However, the intrinsic Ni 3d-O 2p orbital overlapping promotes lattice oxygen release during the Ni valence transition, thereby accelerating structural degradation and interfacial parasitic reactions. Herein, we found that the position-isomer slurry additive lithium 2-thiopheneboron (2LTB) suppresses Ni-O orbital overlap by enhancing the coordination of its Li, B, O, and S atoms with Ni and O in the cathode lattice, thereby stabilizing lattice oxygen at both the initial and deep discharge states. Electroactive 2LTB can form a thin and robust cathode electrolyte interface (CEI) that enhances Li+ diffusion dynamics while alleviating transition metal dissolution, irreversible phase transformation, gas evolution and electrolyte invasion under high voltage. Consequently, LiNi0.8Co0.1Mn0.1O2||Li cells with 1.5 wt.% 2LTB addition exhibits exceptional cycling performances, retaining 82.92% capacity retention after 450 cycles at 1 C and 76.09% after 800 cycles at 5 C under 4.5 V. A 1000-mAh LiNi0.8Co0.1Mn0.1O2-2LTB||graphite pouch cell maintains 81.34% capacity retention after 700 cycles. Our findings establish a versatile framework for leveraging lithiation reagents to regulate orbital interactions, providing both mechanistic insights and practical guidance for the development of high-voltage lithium-ion batteries.
AB - High-voltage nickel-rich layered oxide cathodes have attracted much attention due to their high capacity and elevated voltage plateau. However, the intrinsic Ni 3d-O 2p orbital overlapping promotes lattice oxygen release during the Ni valence transition, thereby accelerating structural degradation and interfacial parasitic reactions. Herein, we found that the position-isomer slurry additive lithium 2-thiopheneboron (2LTB) suppresses Ni-O orbital overlap by enhancing the coordination of its Li, B, O, and S atoms with Ni and O in the cathode lattice, thereby stabilizing lattice oxygen at both the initial and deep discharge states. Electroactive 2LTB can form a thin and robust cathode electrolyte interface (CEI) that enhances Li+ diffusion dynamics while alleviating transition metal dissolution, irreversible phase transformation, gas evolution and electrolyte invasion under high voltage. Consequently, LiNi0.8Co0.1Mn0.1O2||Li cells with 1.5 wt.% 2LTB addition exhibits exceptional cycling performances, retaining 82.92% capacity retention after 450 cycles at 1 C and 76.09% after 800 cycles at 5 C under 4.5 V. A 1000-mAh LiNi0.8Co0.1Mn0.1O2-2LTB||graphite pouch cell maintains 81.34% capacity retention after 700 cycles. Our findings establish a versatile framework for leveraging lithiation reagents to regulate orbital interactions, providing both mechanistic insights and practical guidance for the development of high-voltage lithium-ion batteries.
KW - LiNiCoMnO cathode materials
KW - high voltage
KW - lithium 2-thiopheneboron
KW - lithium-ion batteries
KW - position-isomer lithiation reagents
UR - https://www.scopus.com/pages/publications/105028983147
U2 - 10.1002/aenm.202506157
DO - 10.1002/aenm.202506157
M3 - Article
AN - SCOPUS:105028983147
SN - 1614-6832
VL - 16
JO - Advanced Energy Materials
JF - Advanced Energy Materials
IS - 14
M1 - e06157
ER -