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Lattice Engineering on Li 2 CO 3 ‐Based Sacrificial Cathode Pre‐lithiation Agent for Improving The Energy Density of Li‐Ion Battery Full‐Cell

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Developing sacrificial cathode pre‐lithiation technology to compensate for active lithium loss is vital for improving the energy density of lithium‐ion battery full‐cells. Li 2 CO 3 owns high theoretical specific capacity, superior air stability, but poor conductivity as an insulator, acting as a promising but challenging pre‐lithiation agent candidate. Herein, extracting a trace amount of Co from LiCoO 2 (LCO), we develop a lattice engineering through substituting Li sites with Co and inducing Li defects to obtain Co‐Li 2 CO 3 @LCO, in which both the bandgap and Li‐O bond strength have essentially declined. Benefiting from the synergistic effect of Li defects and bulk phase catalytic regulation of Co, the potential of Li 2 CO 3 deep decomposition significantly decreases from typical >4.7 V to ∼4.25 V versus Li/Li ⁺ , presenting >600 mAh/g compensation capacity. Impressively, coupling 5 wt% Co‐Li 2 CO 3 @LCO within NCM‐811 cathode, 235 Wh/kg pouch‐type full‐cell is achieved, performing 88% capacity retention after 1000 cycles. This article is protected by copyright. All rights reserved
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RESEARCH ARTICLE
www.advmat.de
Lattice Engineering on Li2CO3-Based Sacrificial Cathode
Prelithiation Agent for Improving the Energy Density of
Li-Ion Battery Full-Cell
Yuanlong Zhu, Yilong Chen, Jianken Chen, Jianhua Yin, Zhefei Sun, Guifan Zeng,
Xiaohong Wu, Leiyu Chen, Xiaoyu Yu, Haiyan Luo, Yawen Yan, Haitang Zhang,
Baodan Zhang, Xiaoxiao Kuai, Yonglin Tang, Juping Xu, Wen Yin, Yongfu Qiu,
Qiaobao Zhang, Yu Qiao,* and Shi-Gang Sun
Developing sacrificial cathode prelithiation technology to compensate for
active lithium loss is vital for improving the energy density of lithium-ion
battery full-cells. Li2CO3owns high theoretical specific capacity, superior air
stability, but poor conductivity as an insulator, acting as a promising but
challenging prelithiation agent candidate. Herein, extracting a trace amount
of Co from LiCoO2(LCO), a lattice engineering is developed through
substituting Li sites with Co and inducing Li defects to obtain a composite
structure consisting of (Li0.906Co0.043 0.051)2CO2.934 and ball milled LiCoO2
(Co-Li2CO3@LCO). Notably, both the bandgap and LiO bond strength have
essentially declined in this structure. Benefiting from the synergistic effect of
Li defects and bulk phase catalytic regulation of Co, the potential of Li2CO3
deep decomposition significantly decreases from typical >4.7 to 4.25 V
versus Li/Li+, presenting >600 mAh g1compensation capacity. Impressively,
coupling 5 wt% Co-Li2CO3@LCO within NCM-811 cathode, 235 Wh kg1
pouch-type full-cell is achieved, performing 88% capacity retention after 1000
cycles.
1. Introduction
With the rapid development of electric vehicles and electrochem-
ical energy storage, conventional lithium-ion batteries (LIBs) are
hard to meet the increasing demand for energy density. Solely
Y. Zhu, Y. Chen, J. Chen, J. Yin, G. Zeng, X. Wu, L. Chen, X. Yu, H. Luo,
Y. Yan, H. Zhang, B. Zhang, X. Kuai, Y. Tang, S.-G. Sun
State Key Laboratory of Physical Chemistry of Solid Surfaces
Department of Chemistry
College of Chemistry and Chemical Engineering
Xiamen University
Xiamen 361005, China
Y. Zhu, X. Kuai, Y. Qiao
Fujian Science & Technology Innovation Laboratory for Energy Materials
of China (Tan Kah Kee Innovation Laboratory)
Xiamen 361005, China
E-mail: yuqiao@xmu.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202312159
DOI: 10.1002/adma.202312159
improving the energy density of the cathode
has limited eect on full-cell for practical
application, since the Coulomb eciency
(CE) of the anode in the initial cycle is much
lower than that of the cathode. For anode, it
is well-known that irreversible lithium loss
owes to the formation of solid electrolyte in-
terface (SEI) and lithium metal plating.[]
Therefore, developing prelithiation technol-
ogy to compensate for active lithium loss
(ALL) is critical for improving the energy
density of full-cell.[]According to the dif-
ferent preset positions of Li sources, pre-
lithiation strategies can be mainly divided
into cathode and anode. Although chemi-
cal and electrochemical prelithiated anodes
can address ALL,[]they require additional
procedure and are not suitable for large-
scale manufacture because of high reac-
tivity and safety concerns. Thus, sacrificial
cathode prelithiation agent is proposed to
mitigate ALL in situ by irreversibly releas-
ing active lithium during initial charging.[]
A sacrificial agent should meet four characteristics: ) it must
possess high gravimetric and volumetric capacity so that a small
amount can compensate for ALL; ) in the initial cycle, it should
irreversibly release Li ions within the working voltage range of
Z. Sun, Q. Zhang
Country State Key Laboratory of Physical Chemistry of Solid Surfaces
College of Materials
Xiamen University
Xiamen 361005, China
J. Xu, W. Yin
Institute of High Energy Physics
Chinese Academy of Sciences
Beijing 100049, China
J. Xu, W. Yin
Spallation Neutron Source Science Center
Dongguan 523803, China
Y. Q i u
School of Materials Science and Engineering
Dongguan University of Technology
Guangdong 523808, China
Adv. Mater. 2024,36, 2312159 © 2023 Wiley-VCH GmbH
2312159 (1 of 10)
... In contrast, sacrificial additives in the cathode are more attractive for their high chemical stability. A number of compounds have been reported for sacrificial cathode additives including Li 3 N [ 7 ], Li 3 P [ 8 ], Li 2 CO 3 [ 9 ], Li 4 SiO 4 [ 10 ], Li 2 C 2 O 4 [ 11 ], Li 2 C 4 O 4 [ 12 ], Li 5 FeO 4 [ 13 ], and Li 6 CoO 4 [ 14 ] and composites of LiF [ 15 ], Li 2 O [ 16 ], and Li 2 S [ 17 ] with metals such as Co and Fe. However, their commercial applications are hindered by severe problems including high electrochemical decomposition potential and mass residues. ...
... However, their commercial applications are hindered by severe problems including high electrochemical decomposition potential and mass residues. For instance, Li 2 CO 3 is insulating and difficult to be decomposed below 4.0 V (versus Li + /Li) even with cobalt (Co) modification [ 9 ]. These severely limit the viable additives. ...
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