Enhancing reversible capacity and cycling stability of Li1.2Ni0.13Fe0.13Mn0.54O2 by inducing low Li/Ni misalignment through Mo doping

Ran Pei-Lin; Wu Kang; Zhao En-Yue; Wang Fang-Wei; Wu Zhi-Min

doi:10.7498/aps.73.20231361

Abstract

Li-ion batteries (LIBs) are widely used in mobile devices and electric vehicles, but the traditional layered transition metal cathode material, LiTMO₂(TM=Ni, Co, Mn, or Al), has a low energy density that cannot satisfy the demand of commercial applications. The Li-rich Mn-based layered oxides (LRLOs) are a strong competitor to the traditional layered cathode materials for their specific capacity of more than 200 mAh/g. Due to the high energy density and low cost, Li-rich Mn-based layered oxides (LRLO) have been a promising candidate cathode for next-generation Li-ion batteries. The anionic redox reaction (ARR) in LRLO destabilizes the lattice oxygen, leading to voltage degradation and capacity loss. Although iron-substituted cobalt-free Li-rich materials can achieve less voltage decay, they suffer severe cation disorder and poor kinetics. Here, we develop a simple and feasible high-valent ion doping strategy by doping Mo into Li_1.2Ni_0.13Fe_0.13Mn_0.54O₂(LNFMO), which expands the Li layer spacing and provides a broader channel for Li⁺ transport, thereby improving the diffusion kinetics of Li⁺, effectively suppressing the cation disorder, and further stabilizing the layered structure. As a result, the Mo-doped LRLO exhibits significantly enhanced electrochemical performance, with an initial reversible capacity of 209.48 mAh/g at 0.2 C, and the initial specific capacity increasing from 137.02 mAh/g to 165.15 mAh/g at 1 C. After 300 cycles, specific capacity remains 117.49 mAh/g for the Mo-doped cathode, and the voltage decay decreases from 2.09 mV/cycle to 1.66 mV/cycle. The Mo-doped LRLO is systematically characterized, and the mechanism of cycle stabilization is revealed, which provides an important reference for designing high performance Li-rich cathode.

Keywords:

Authors and contacts

1.
College of Physics and Electronic Engineering, Chongqing Normal University, Chongqing 401331, China
2.
Songshan Lake Materials Laboratory, Dongguan 523808, China
3.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Zhao En-Yue, eyzhao@sslab.org.cn ; Wang Fang-Wei, fwwang@iphy.ac.cn ; Wu Zhi-Min, zmwu@cqnu.edu.cn

Funds: Project supported by the Key Project of Scientific and Technological Research Program of Chongqing Municipal Education Commission of China (Grant No. KJZD-K202300512) and the National Natural Science Foundation of China (Grant Nos. 52088101, 12105197).

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References

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图 1 Rietveld精修的样品LNFMO (a)和LNFMO-Mo (d) XRD图谱; 样品LNFMO (b)和LNFMO-Mo (e)的SEM图; 样品LNFMO (c)和LNFMO-Mo (f)的TEM图及层间距; LNFMO-Mo (g)表面不同元素的EDS分布图

Figure 1. Rietveld refined XRD patterns of samples LNFMO (a) and LNFMO-Mo (d); SEM images of samples LNFMO (b) and LNFMO-Mo (e); TEM images and layer spacing of samples LNFMO (c) and LNFMO-Mo (f); EDS images of distributions of different elements on the surface of LNFMO-Mo (g).

DownLoad: Full-Size Img PowerPoint

图 2 样品LNFMO (a)和LNFMO-Mo (b)前3次循环的CV曲线; 在不同电流密度下的倍率性能 (c); 0.2 C电流密度下的初始循环曲线 (d); LNFMO (e)和LNFMO-Mo (f)的GITT曲线; 两种样品0.2 C (g)、0.5 C (h)、1 C (i)电流密度下的长循环性能

Figure 2. CV curves for the first 3 cycles of samples LNFMO (a) and LNFMO-Mo (b); rate performance at different current density (c); initial cycling curves at 0.2 C current density (d); GITT curves of samples LNFMO (e) and LNFMO-Mo (f); the long-cycle performance of the two samples at 0.2 C (g), 0.5 C (h), and 1 C (i) current density.

DownLoad: Full-Size Img PowerPoint

图 3 LNFMO (a)和LNFMO-Mo (b)在原始、第1次充电至4.5 V、 4.8 V, 第1次放电至2.0 V状态下的XRD谱图及I_(003)/(104)比值的变化; LNFMO(c)和LNFMO-Mo(d)在原始、第1次充电至4.8 V, 第1次放电至2.0 V状态下的O 1s XPS光谱

Figure 3. XRD spectra of LNFMO (a) and LNFMO-Mo (b) in the pristine, first charge to 4.5 V, 4.8 V, and first discharge to 2.0 V states and the variation of the I_(003)/(104) ratio; O 1s XPS spectra of LNFMO (c) and LNFMO-Mo (d) in the pristine, first charge to 4.8 V, and first discharge to 2.0 V states.

DownLoad: Full-Size Img PowerPoint

[1]	Chen Q, Pei Y, Chen H, Song Y, Zhen L, Xu C Y, Xiao P, Henkelman G 2020 Nat. Commun. 11 3411 Google Scholar
[2]	He W, Zhang C, Wang M, Wei B, Zhu Y, Wu J, Liang C, Chen L, Wang P, Wei W 2022 Adv. Funct. Mater. 32 2200322 Google Scholar
[3]	Seo D-H, Lee J, Urban A, Malik R, Kang S, Ceder G 2016 Nat. Chem. 8 692 Google Scholar
[4]	Li X, Li X, Monluc L, et al. 2022 Adv. Energy Mater. 12 2200427 Google Scholar
[5]	Jiao J, Zhang Z, Kuroiwa Y, Zhao E, Yin W, Wang B, Wang F, Zhao J, Zhang X, Xiao X 2023 Chem. Eng. J. 454 140327 Google Scholar
[6]	Zhang K, Li B, Zuo Y, Song J, Shang H, Ning F, Xia D 2019 Electrochem. Energy Rev. 2 606 Google Scholar
[7]	Eum D, Kim B, Kim S J, et al. 2020 Nat. Mater. 19 419 Google Scholar
[8]	Liu W, Li J, Li W, Xu H, Zhang C, Qiu X 2020 Nat. Commun. 11 3629 Google Scholar
[9]	Asl H Y, Manthiram A 2020 Science 369 140 Google Scholar
[10]	Manthiram A, Knight J C, Myung S T, Oh S-M, Sun Y K 2016 Energy Mater. 6 1501010 Google Scholar
[11]	Wu K, Zhao E, Ran P, Yin W, Zhang Z, Wang B, Ikeda K, Otomo T, Xiao X, Wang F, Zhao J 2023 Small 19 2300419 Google Scholar
[12]	Hu S, Pillai Anoop S, Liang G, Pang W K, Wang H, Li Q, Guo Z 2019 Electrochem. Energy Rev. 2 277 Google Scholar
[13]	Zhao H, Lam W A, Sheng L, Wang L, Bai P, Yang Y, Ren D, Xu H, He X 2022 Adv. Energy Mater. 12 2103894 Google Scholar
[14]	Zhao E, Zhang M, Wang X, et al. 2020 Energy Storage Mater. 24 384 Google Scholar
[15]	Zhao H, Li W, Li J, Xu H, Zhang C, Li J, Han C, Li Z, Chu M, Qiu X 2022 Nano Energy 92 106760 Google Scholar
[16]	Billaud J, Sheptyakov D, Sallard S, Leanza D, Talianker M, Grinblat J, Sclar H, Aurbach D, Novák P, Villevieille C 2019 J. Mater. Chem. A 7 15215 Google Scholar
[17]	Zhao T, Ji R, Yang H, Zhang Y, Sun X, Li Y, Li L, Chen R 2019 J. Energy Chem. 33 37 Google Scholar
[18]	Lee Y, Park H, Cho M, Ahn J, Ko W, Kang J, Choi Y J, Kim H, Park I, Ryu W, Hong J, Kim J 2022 Adv. Funct. Mater. 32 2204354 Google Scholar
[19]	Nayak P K, Grinblat J, Levi M, Levi E, Kim S, Choi J W, Aurbach D 2016 Adv. Energy Mater. 6 1502398 Google Scholar
[20]	Dahiya P P, Ghanty C, Sahoo K, Basu S, Majumder S B 2018 J. Electrochem. Soc. 165 A3114 Google Scholar
[21]	Wang E, Xiao D, Wu T, Liu X, Zhou Y, Wang B, Lin T, Zhang X, Yu H 2022 Adv. Funct. Mater. 32 2201744 Google Scholar
[22]	Kroger F A 1977 Annu. Rev. Mater. Sci. 7 449 Google Scholar
[23]	Zu C X, Li H 2011 Energy Environ. Sci. 4 2614 Google Scholar
[24]	Li X, Xin H, Liu Y, Li D, Yuan X, Qin X 2015 RSC Adv. 5 45351 Google Scholar
[25]	Liu X, Yu B, Wang M, Jin Y, Fu Z, Chen J, Ma Z, Guo B, Huang Y, Li X 2022 Mater. Today Commun. 32 104170 Google Scholar
[26]	Yang J, Chen Y, Li Y, Xi X, Zheng J, Zhu Y, Xiong Y, Liu S 2021 ACS Appl. Mater. Interfaces 13 25981 Google Scholar
[27]	Meng J, Xu L, Ma Q, Yang M, Fang Y, Wan G, Li R, Yuan J, Zhang X, Yu H, Liu L, Liu T 2022 Adv. Funct. Mater. 32 2113013 Google Scholar
[28]	Morales J, Pérez-Vicente C, Tirado J L 1990 Mater. Res. Bull. 25 623 Google Scholar
[29]	Zhao J, Zhang W, Huq A, Misture S T, Zhang B, Guo S, Wu L, Zhu Y, Chen Z, Amine K, Pan F, Bai J, Wang F 2017 Adv. Energy Mater. 7 1601266 Google Scholar
[30]	Li Q, Wang Y, Wang X, Sun X, Zhang J N, Yu X, Li H 2020 ACS Appl. Mater. Interfaces 12 2319 Google Scholar

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Enhancing reversible capacity and cycling stability of Li_1.2Ni_0.13Fe_0.13Mn_0.54O₂ by inducing low Li/Ni misalignment through Mo doping