富锂正极材料Li1.2Mn0.54Co0.13Ni0.13NaxO2表面结构的电子显微分析

doi:10.3866/PKU.WHXB201605164

Abstract

Abstract:

In this work, Li_1.2Mn_0.54Co_0.13Ni_0.13Na_xO₂ was prepared via an ion-exchange process combined with a solid-state reaction. Aberration-corrected scanning transmission electron microscopy (STEM), energydispersive X-ray spectroscopy (EDS), and electron energy loss spectroscopy (EELS) were all used to study the surface structure and chemical distribution of the resulting material. Nickel (Ni) was found to be enriched at the surface in regions perpendicular to the lithium diffusion channels (that is, the (200) surfaces) and also exhibited a tendency to diffuse into the lithium (Li) layers, generating a Fm3m rocksalt phase. In contrast, cobalt (Co) segregated along the transition metal (TM) layers of the (001) and (200) surfaces. The results of aging trials demonstrated that Co-enriched layers lead to surface structure instability, as evidenced by the formation of a large number of antisite defects (Li-TM) and rocksalt phase structures at the (001) surface during aging.

Key words: Lithium ion battery, Cathode material, Lithium rich cathode material, Surface segregation, Scanning transmission electron microscopy

Wei HUANG,Chun-Yang WU,Yue-Wu ZENG,Chuan-Hong JIN,Ze ZHANG. Surface Analysis of the Lithium-Rich Cathode Material Li_1.2Mn_0.54Co_0.13Ni_0.13Na_xO₂ by Advanced Electron Microscopy[J]. Acta Phys. -Chim. Sin. 2016, 32(9), 2287-2292. doi: 10.3866/PKU.WHXB201605164

References

1	Sun Y. K. ; Myung S. T. ; Park B. C. ; Prakash J. ; Belharouak I. ; Amine K. Nat. Mater 2009, 8, 320.
2	Armstrong A. R. ; Bruce P. G. Nature 1996, 381, 499.
3	Ohzuku T. ; Makimura Y. Chem. Lett 2001, (No. 7), 642.
4	Kim J. S. ; Johnson C. S. ; Vaughey J. T. ; Thackeray M. M. ; Hackney S. A. Chem. Mater 2004, 16, 1996.
5	Thackeray M. M. ; Kang S. H. ; Johnson C. S. ; Vaughey J. T. ; Benedek R. ; Hackney S. A. J. Mater. Chem 2007, 17, 3112.
6	Shi S. J. ; Tu J. P. ; Tang Y. Y. ; Yu Y. X. ; Zhang Y. Q. ; Wang X. L. ; Gu C. D. J. Power Sources 2013, 228, 14.
7	Li Q. ; Li G. S. ; Fu C. C. ; Luo D. ; Fan J. M. ; Li L. P. ACS Appl. Mater. Inter 2014, 6, 10330.
8	Chen L. ; Chen S. ; Hu D. Z. ; Su Y. F. ; Li W. K. ; Wang Z. ; Bao L. Y. ; Wu F. Acta Phys. -Chim. Sin 2014, 30, 467.
8	陈来; 陈实; 胡道中; 苏岳锋; 李维康; 王昭; 包丽颖; 吴锋. 物理化学学报, 2014, 30, 467.
9	Ren X. Z. ; Liu T. ; Sun L. N. ; Zhang P. X. Acta Phys. -Chim. Sin 2014, 30, 1641.
9	任祥忠; 刘涛; 孙灵娜; 张培新. 物理化学学报, 2014, 30, 1641.
10	Croy J. R. ; Kim D. ; Balasubramanian M. ; Gallagher K. ; Kang S. H. ; Thackeray M. M. J. Electrochem. Soc 2012, 159, A781.
11	Gu M. ; Belharouak I. ; Zheng J. M. ; Wu H. M. ; Xiao J. ; Genc A. ; Amine K. ; Thevuthasan S. ; Baer D. R. ; Zhang J. G. ; Browning N. D. ; Liu J. ; Wang C. M. ACS Nano 2013, 7, 760.
12	Boulineau A. ; Simonin L. ; Colin J. F. ; Bourbon C. ; Patoux S. Nano Lett 2013, 13, 3857.
13	Boulineau A. ; Simonin L. ; Colin J. F. ; Canevet E. ; Daniel L. ; Patoux S. Chem. Mater 2012, 24, 3558.
14	Lin F. ; Markus I. M. ; Nordlund D. ; Weng T. C. ; Asta M. D. ; Xin H. L. L. ; Doeff M. M. Nat. Commun 2014, 5, 3529.
15	Zheng J. M. ; Gu M. ; Genc A. ; Xiao J. ; Xu P. H. ; Chen X. L. ; Zhu Z. H. ; Zhao W. B. ; Pullan L. ; Wang C. M. ; Zhang J. G. Nano Lett 2014, 14, 2628.
16	Gu M. ; Belharouak I. ; Genc A. ; Wang Z. G. ; Wang D. P. ; Amine K. ; Gao F. ; Zhou G.W. ; Thevuthasan S. ; Baer D. R. ; Zhang J. G. ; Browning N. D. ; Liu J. ; Wang C. M. Nano Lett 2012, 12, 5186.
17	Gu M. ; Genc A. ; Belharouak I. ; Wang D. P. ; Amine K. ; Thevuthasan S. ; Baer D. R. ; Zhang J. G. ; Browning N. D. ; Liu J. ; Wang C. M. Chem. Mater 2013, 25, 2319.
18	Kim D. ; Kang S. H. ; Balasubramanian M. ; Johnson C. S. Electrochem. Commun 2010, 12, 1618.
19	Yan P. F. ; Zheng J. M. ; Lv D. P. ; Wei Y. ; Zheng J. X. ; Wang Z. G. ; Kuppan S. ; Yu J. G. ; Luo L. L. ; Edwards D. ; Olszta M. ; Amine K. ; Liu J. ; Xiao J. ; Pan F. ; Chen G. Y. ; Zhang J.G. ; Wang C. M. Chem. Mater 2015, 27, 5393.
20	Jarvis K. A. ; Deng Z. Q. ; Allard L. F. ; Manthiram A. ; Ferreira P. J. Chem. Mater 2011, 23, 3614.
21	Yu H. J. ; Ishikawa R. ; So Y. G. ; Shibata N. ; Kudo T. ; Zhou H. S. ; Ikuhara Y. Angew. Chem. Int. Edit 2013, 52, 5969.
22	Jarvis K. A. ; Deng Z. ; Allard L. F. ; Manthiram A. ; Ferreira P.J. J. Mater. Chem 2012, 22, 11550.
23	Yan P. F. ; Zheng J. M. ; Zheng J. X. ; Wang Z. G. ; Teng G. F. ; Kuppan S. ; Xiao J. ; Chen G. Y. ; Pan F. ; Zhang J. G. ; Wang C. M. Adv. Energy Mater 2016, 6, 1502455.
24	Graetz J. ; Ahn C. C. ; Ouyang H. ; Rez P. ; Fultz B. Phys. Rev. B 2004, 69, 235103.
25	Pearson D. H. ; Ahn C. C. ; Fultz B. Phys. Rev. B 1993, 47, 8471.
26	Varela M. ; Oxley M. P. ; Luo W. ; Tao J. ; Watanabe M. ; Lupini A. R. ; Pantelides S. T. ; Pennycook S. J. Phys. Rev. B 2009, 79, 085117.
27	Huang Z. F. ; Du F. ; Wang C. Z. ; Wang D. P. ; Chen G. Phys. Rev. B 2007, 75, 054411.
28	Yamada A. ; Tanaka M. ; Tanaka K. ; Sekai K. J. Power Sources 1999, 81, 73.

[1]	Hangyu Lu, Ruilin Hou, Shiyong Chu, Haoshen Zhou, Shaohua Guo. Progress on Modification Strategies of Layered Lithium-Rich Cathode Materials for High Energy Lithium-Ion Batteries [J]. Acta Phys. -Chim. Sin., 2023, 39(7): 2211057-0.
[2]	Qilong Feng, Chongzhi Zhu, Guan Sheng, Tulai Sun, Yonghe Li, Yihan Zhu. Four-Dimensional Scanning Transmission Electron Microscopy: From Material Microstructures to Physicochemical Properties [J]. Acta Phys. -Chim. Sin., 2023, 39(3): 2210017-0.
[3]	Yae Qi, Yongyao Xia. Electrolyte Regulation Strategies for Improving the Electrochemical Performance of Aqueous Zinc-Ion Battery Cathodes [J]. Acta Phys. -Chim. Sin., 2023, 39(2): 2205045-0.
[4]	Feng Wu, Qing Li, Lai Chen, Zirun Wang, Gang Chen, Liying Bao, Yun Lu, Shi Chen, Yuefeng Su. An Optimized Synthetic Process for the Substitution of Cobalt in Nickel-Rich Cathode Materials [J]. Acta Phys. -Chim. Sin., 2022, 38(5): 2007017-.
[5]	Xiaobo Ding, Qianhui Huang, Xunhui Xiong. Research and Application of Fast-Charging Graphite Anodes for Lithium-Ion Batteries [J]. Acta Phys. -Chim. Sin., 2022, 38(11): 2204057-.
[6]	Yuefeng Su, Qiyu Zhang, Lai Chen, Liying Bao, Yun Lu, Shi Chen, Feng Wu. Effects of ZrO₂ Coating on Ni-Rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathodes with Enhanced Cycle Stabilities [J]. Acta Phys. -Chim. Sin., 2021, 37(3): 2005062-.
[7]	Yongli Heng, Zhenyi Gu, Jinzhi Guo, Xinglong Wu. Research Progresses on Vanadium-Based Cathode Materials for Aqueous Zinc-Ion Batteries [J]. Acta Phys. -Chim. Sin., 2021, 37(3): 2005013-.
[8]	Jiangtao Huang, Jiang Zhou, Shuquan Liang. Guest Pre-Intercalation Strategy to Boost the Electrochemical Performance of Aqueous Zinc-Ion Battery Cathodes [J]. Acta Phys. -Chim. Sin., 2021, 37(3): 2005020-.
[9]	Sidong Zhang, Yuan Liu, Muyao Qi, Anmin Cao. Localized Surface Doping for Improved Stability of High Energy Cathode Materials [J]. Acta Phys. -Chim. Sin., 2021, 37(11): 2011007-.
[10]	Yaokun Ye, Zongxiang Hu, Jiahua Liu, Weicheng Lin, Taowen Chen, Jiaxin Zheng, Feng Pan. Research Progress of Theoretical Studies on Polarons in Cathode Materials of Lithium-Ion Batteries [J]. Acta Phys. -Chim. Sin., 2021, 37(11): 2011003-.
[11]	Yongli Tong, Meizhen Dai, Lei Xing, Hengqi Liu, Wanting Sun, Xiang Wu. Asymmetric Hybrid Capacitor Based on NiCo₂O₄ Nanosheets Electrode [J]. Acta Physico-Chimica Sinica, 2020, 36(7): 1903046-.
[12]	Xinxin Cao,Jiang Zhou,Anqiang Pan,Shuquan Liang. Recent Advances in Phosphate Cathode Materials for Sodium-ion Batteries [J]. Acta Physico-Chimica Sinica, 2020, 36(5): 1905018-.
[13]	Yongchao Shi, Mingxue Tang. NMR/EPR Investigation of Rechargeable Batteries [J]. Acta Physico-Chimica Sinica, 2020, 36(4): 1905004-.
[14]	Zhenjie CHENG, Yayun MAO, Qingyu DONG, Feng JIN, Yanbin SHEN, Liwei CHEN. Fluoroethylene Carbonate as an Additive for Sodium-Ion Batteries: Effect on the Sodium Cathode [J]. Acta Physico-Chimica Sinica, 2019, 35(8): 868-875.
[15]	Dong CHEN,Xinyang YUE,Xunlu LI,Xiaojing WU,Yongning ZHOU. Research Progress of Cathode Materials for Lithium-Selenium Batteries [J]. Acta Phys. -Chim. Sin., 2019, 35(7): 667-683.

Surface Analysis of the Lithium-Rich Cathode Material Li_1.2Mn_0.54Co_0.13Ni_0.13Na_xO₂ by Advanced Electron Microscopy

RichHTML

PDF

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Metrics

Recommended 0

Surface Analysis of the Lithium-Rich Cathode Material Li1.2Mn0.54Co0.13Ni0.13NaxO2 by Advanced Electron Microscopy

RichHTML

PDF

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Metrics

Recommended 0

Surface Analysis of the Lithium-Rich Cathode Material Li_1.2Mn_0.54Co_0.13Ni_0.13Na_xO₂ by Advanced Electron Microscopy