TY - JOUR
T1 - Fast and Durable Lithium Storage Enabled by Tuning Entropy in Wadsley–Roth Phase Titanium Niobium Oxides
AU - Zheng, Jie
AU - Xia, Rui
AU - Sun, Congli
AU - Yaqoob, Najma
AU - Qiu, Qianyuan
AU - Zhong, Liping
AU - Li, Yongdan
AU - Kaghazchi, Payam
AU - Zhao, Kangning
AU - ten Elshof, Johan E.
AU - Huijben, Mark
N1 - Funding Information:
J.Z. and R.X. contributed equally to this work. J.Z., R.X., and Q.Q. acknowledge the financial support of the China Scholarships Council (CSC) program, no. 201906150132, no. 201807720013, and no. 201906150134, respectively. The STEM analysis was supported by the National Natural Science Foundation of China (22005230).
Publisher Copyright:
© 2023 The Authors. Small published by Wiley-VCH GmbH.
PY - 2023/7/26
Y1 - 2023/7/26
N2 - Wadsley–Roth phase titanium niobium oxides have received considerable interest as anodes for lithium ion batteries. However, the volume expansion and sluggish ion/electron transport kinetics retard its application in grid scale. Here, fast and durable lithium storage in entropy-stabilized Fe0.4Ti1.6Nb10O28.8 (FTNO) is enabled by tuning entropy via Fe substitution. By increasing the entropy, a reduction of the calcination temperature to form a phase pure material is achieved, leading to a reduced grain size and, therefore, a shortening of Li+ pathway along the diffusion channels. Furthermore, in situ X-ray diffraction reveals that the increased entropy leads to the decreased expansion along a–axis, which stabilizes the lithium intercalation channel. Density functional theory modeling indicates the origin to be the more stable Fe-O bond as compared to Ti-O bond. As a result, the rate performance is significantly enhanced exhibiting a reversible capacity of 73.7 mAh g−1 at 50 C for FTNO as compared to 37.9 mAh g−1 for its TNO counterpart. Besides, durable cycling is achieved by FTNO, which delivers a discharge capacity of 130.0 mAh g−1 after 6000 cycles at 10 C. Finally, the potential impact for practical application of FTNO anodes has been demonstrated by successfully constructing fast charging and stable LiFePO4‖FTNO full cells.
AB - Wadsley–Roth phase titanium niobium oxides have received considerable interest as anodes for lithium ion batteries. However, the volume expansion and sluggish ion/electron transport kinetics retard its application in grid scale. Here, fast and durable lithium storage in entropy-stabilized Fe0.4Ti1.6Nb10O28.8 (FTNO) is enabled by tuning entropy via Fe substitution. By increasing the entropy, a reduction of the calcination temperature to form a phase pure material is achieved, leading to a reduced grain size and, therefore, a shortening of Li+ pathway along the diffusion channels. Furthermore, in situ X-ray diffraction reveals that the increased entropy leads to the decreased expansion along a–axis, which stabilizes the lithium intercalation channel. Density functional theory modeling indicates the origin to be the more stable Fe-O bond as compared to Ti-O bond. As a result, the rate performance is significantly enhanced exhibiting a reversible capacity of 73.7 mAh g−1 at 50 C for FTNO as compared to 37.9 mAh g−1 for its TNO counterpart. Besides, durable cycling is achieved by FTNO, which delivers a discharge capacity of 130.0 mAh g−1 after 6000 cycles at 10 C. Finally, the potential impact for practical application of FTNO anodes has been demonstrated by successfully constructing fast charging and stable LiFePO4‖FTNO full cells.
KW - Entropy
KW - Fast charging
KW - Iron substitution
KW - Lithium-ion batteries
KW - Wadsley–Roth phase
KW - UT-Hybrid-D
UR - http://www.scopus.com/inward/record.url?scp=85151635951&partnerID=8YFLogxK
U2 - 10.1002/smll.202301967
DO - 10.1002/smll.202301967
M3 - Article
AN - SCOPUS:85151635951
SN - 1613-6810
VL - 19
JO - Small
JF - Small
IS - 30
M1 - 2301967
ER -