Citation: Yang Chun, Gong Zhengliang, Zhao Wengao, Yang Yong. Synthesis and Electrochemical Performance of Lithium Rich Cathode Materials xLi₃NbO₄·(1-x)LiMO₂ (M=Mn, Co; 0 ＜ x＜1) for Li-ion Batteries[J]. Acta Chimica Sinica, ;2017, 75(2): 212-217. doi: 10.6023/A16050240 shu

Synthesis and Electrochemical Performance of Lithium Rich Cathode Materials xLi₃NbO₄·(1-x)LiMO₂ (M=Mn, Co; 0 ＜ x＜1) for Li-ion Batteries

Yang Chun ^a ,
Gong Zhengliang ^a,*,, ,
Zhao Wengao ^a ,
Yang Yong ^a,b,*,,

a.
College of Energy, Xiamen University, Xiamen 361005
b.
State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005

Corresponding author: Gong Zhengliang, zlgong@xmu.edu.cn Yang Yong, yyang@xmu.edu.cn
Received Date: 16 May 2016
Revised Date: 7 October 2016

Fund Project: Project supported by the National Natural Science Foundation of China 21233004, 21473148, 21428303Natural Science Foundation of Fujian Province 2014J05019

Figures(10)

Lithium rich material xLi₃NbO₄·(1-x) LiMnO₂ (0 ＜ x <1) was successfully synthesized by solid state method. Stoichiometric amounts of Li₂CO₃, Mn₂O₃ and Nb₂O₅ were mixed by ball milling, and the mixture was calcinated at 900℃ for 5 h under Ar atmosphere. X-ray diffraction (XRD) results indicate that the samples with 0.25 ＜ x <0.67 can be indexed as a cubic structure with Fm-3m space group. Electrochemical results show that the samples of x=0.25 and 0.43 have better electrochemical performance, both delivering 216 mAh·g^-1 in the initial cycle between 2 V and 4.8 V. Although voltage decay is an intrinsic drawback of lithium excess materials, the sample of x=0.43 decays slower. We speculate that Li₃NbO₄ helps stabilizing the crystal structure. Ex-situ XPS and XAS studies show that the charging process can be divided into two stages. In the first stage, below 4.3 V, Mn³⁺ is oxidized to Mn⁴⁺, in the second stage, O^2- is oxidized. The reversible oxidation of O^2- is the origin of the achievement of large reversible capacity. Co³⁺ doped material 0.43Li₃NbO₄·0.57LiMn_1-yCo_yO₂ (y=0.25; 0.5) was also synthesized by the same procedure. The structure of the doped material maintains the cubic structure with smaller lattice constant and the variation of lattice constant is in proportion to the amount of Co³⁺. Galvanostatic charge and discharge tests show that 0.43Li₃NbO₄·0.57LiMn_0.75Co_0.25O₂ also delivers a large capacity of 215 mAh·g^-1 in the first cycle between 2 V and 4.8 V, but the voltage plateau in the charging process decreased from 4.3 V to 4.1 V, it can be attributed to the weak dissociation energy of Mn-O bond and the overlap of Co^3+/4+ 3d and O^2- 2p energy band. The electrochemical impedance spectroscopy results show that a moderate amount of Co³⁺ doped into the material decreases the charge transfer resistance. After doped with Co³⁺, the rate capability is improved.
- lithium-ion batteries,
- Li₃NbO₄,
- rock-salt structure,
- lithium excess materials,
- electrochemical performance
1. [1]
  Tarascon, J.-M.; Armand, M. Nature 2001, 414(6861), 359.
2. [2]
  Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D. Energy Environ. Sci. 2011, 4(9), 3243.
3. [3]
4. [4]
5. [5]
6. [6]
  Ukei, K.; Suzuki, H.; Shishido, T.; Fukuda, T. Acta Crystallogr. C 1994, 50(5), 655.
7. [7]
  Yabuuchi, N.; Takeuchi, M.; Endo, D.; Ozaki, T.; Inamasu, T.; Son, J.-Y.; Cui, Y.-T.; Oji, H.; Komaba, S. Meet. Abstr. 2013, MA2013-02(12), 874.
8. [8]
  Yabuuchi, N.; Takeuchi, M.; Nakayama, M.; Shiiba, H.; Ogawa, M.; Nakayama, K.; Ohta, T.; Endo, D.; Ozaki, T.; Inamasu, T.; Sato, K.; Komaba, S. Proc. Natl. Acad. Sci. 2015, 112(25), 7650.
9. [9]
  Sathiya, M.; Abakumov, A. M.; Foix, D.; Rousse, G.; Ramesha, K.; Saubanère, M.; Doublet, M. L.; Vezin, H.; Laisa, C. P.; Prakash, A. S.; Gonbeau, D.; VanTendeloo, G.; Tarascon, J.-M. Nat. Mater. 2015, 14(2), 230.
10. [10]
11. [11]
  Deng, Z. Q.; Manthiram, A. J. Phys. Chem. C 2011, 115(14), 7097.
1. [1]
  Qi Li , Pingan Li , Zetong Liu , Jiahui Zhang , Hao Zhang , Weilai Yu , Xianluo Hu . Fabricating Micro/Nanostructured Separators and Electrode Materials by Coaxial Electrospinning for Lithium-Ion Batteries: From Fundamentals to Applications. Acta Physico-Chimica Sinica, 2024, 40(10): 2311030-. doi: 10.3866/PKU.WHXB202311030
2. [2]
  Xinpeng LIU , Liuyang ZHAO , Hongyi LI , Yatu CHEN , Aimin WU , Aikui LI , Hao HUANG . Ga₂O₃ coated modification and electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1105-1113. doi: 10.11862/CJIC.20230488
3. [3]
  Jiahong ZHENG , Jiajun SHEN , Xin BAI . Preparation and electrochemical properties of nickel foam loaded NiMoO₄/NiMoS₄ composites. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 581-590. doi: 10.11862/CJIC.20230253
4. [4]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115
5. [5]
  Yuanchao LI , Weifeng HUANG , Pengchao LIANG , Zifang ZHAO , Baoyan XING , Dongliang YAN , Li YANG , Songlin WANG . Effect of heterogeneous dual carbon sources on electrochemical properties of LiMn_0.8Fe_0.2PO₄/C composites. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 751-760. doi: 10.11862/CJIC.20230252
6. [6]
  Yifeng Xu , Jiquan Liu , Bin Cui , Yan Li , Gang Xie , Ying Yang . “Xiao Li’s School Adventures: The Working Principles and Safety Risks of Lithium-ion Batteries”. University Chemistry, 2024, 39(9): 259-265. doi: 10.12461/PKU.DXHX202404009
7. [7]
  Kun Xu , Xinxin Song , Zhilei Yin , Jian Yang , Qisheng Song . Comprehensive Experimental Design of Preferential Orientation of Zinc Metal by Heat Treatment for Enhanced Electrochemical Performance. University Chemistry, 2024, 39(4): 192-197. doi: 10.3866/PKU.DXHX202309050
8. [8]
  Siyu Zhang , Kunhong Gu , Bing'an Lu , Junwei Han , Jiang Zhou . Hydrometallurgical Processes on Recycling of Spent Lithium-lon Battery Cathode: Advances and Applications in Sustainable Technologies. Acta Physico-Chimica Sinica, 2024, 40(10): 2309028-. doi: 10.3866/PKU.WHXB202309028
9. [9]
  Zhihuan XU , Qing KANG , Yuzhen LONG , Qian YUAN , Cidong LIU , Xin LI , Genghuai TANG , Yuqing LIAO . Effect of graphene oxide concentration on the electrochemical properties of reduced graphene oxide/ZnS. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1329-1336. doi: 10.11862/CJIC.20230447
10. [10]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189
11. [11]
  Zhenming Xu , Mingbo Zheng , Zhenhui Liu , Duo Chen , Qingsheng Liu . Experimental Design of Project-Driven Teaching in Computational Materials Science: First-Principles Calculations of the LiFePO₄ Cathode Material for Lithium-Ion Batteries. University Chemistry, 2024, 39(4): 140-148. doi: 10.3866/PKU.DXHX202307022
12. [12]
  Qin ZHU , Jiao MA , Zhihui QIAN , Yuxu LUO , Yujiao GUO , Mingwu XIANG , Xiaofang LIU , Ping NING , Junming GUO . Morphological evolution and electrochemical properties of cathode material LiAl_0.08Mn_1.92O₄ single crystal particles. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1549-1562. doi: 10.11862/CJIC.20240022
13. [13]
  Jiahong ZHENG , Jingyun YANG . Preparation and electrochemical properties of hollow dodecahedral CoNi₂S₄ supported by MnO₂ nanowires. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1881-1891. doi: 10.11862/CJIC.20240170
14. [14]
  Hongyi LI , Aimin WU , Liuyang ZHAO , Xinpeng LIU , Fengqin CHEN , Aikui LI , Hao HUANG . Effect of Y(PO₃)₃ double-coating modification on the electrochemical properties of Li[Ni_0.8Co_0.15Al_0.05]O₂. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1320-1328. doi: 10.11862/CJIC.20230480
15. [15]
  Jianbao Mei , Bei Li , Shu Zhang , Dongdong Xiao , Pu Hu , Geng Zhang . Enhanced Performance of Ternary NASICON-Type Na_3.5-xMn_0.5V_1.5-xZr_x(PO₄)₃/C Cathodes for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(12): 2407023-. doi: 10.3866/PKU.WHXB202407023
16. [16]
  Qingyan JIANG , Yanyong SHA , Chen CHEN , Xiaojuan CHEN , Wenlong LIU , Hao HUANG , Hongjiang LIU , Qi LIU . Constructing a one-dimensional Cu-coordination polymer-based cathode material for Li-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 657-668. doi: 10.11862/CJIC.20240004
17. [17]
  Jie XIE , Hongnan XU , Jianfeng LIAO , Ruoyu CHEN , Lin SUN , Zhong JIN . Nitrogen-doped 3D graphene-carbon nanotube network for efficient lithium storage. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1840-1849. doi: 10.11862/CJIC.20240216
18. [18]
  Doudou Qin , Junyang Ding , Chu Liang , Qian Liu , Ligang Feng , Yang Luo , Guangzhi Hu , Jun Luo , Xijun Liu . Addressing Challenges and Enhancing Performance of Manganese-based Cathode Materials in Aqueous Zinc-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(10): 2310034-. doi: 10.3866/PKU.WHXB202310034
19. [19]
  Yong Zhou , Jia Guo , Yun Xiong , Luying He , Hui Li . Comprehensive Teaching Experiment on Electrochemical Corrosion in Galvanic Cell for Chemical Safety and Environmental Protection Course. University Chemistry, 2024, 39(7): 330-336. doi: 10.3866/PKU.DXHX202310109
20. [20]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(1761)
HTML views(196)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis and Electrochemical Performance of Lithium Rich Cathode Materials xLi3NbO4·(1-x)LiMO2 (M=Mn, Co; 0 ＜ x＜1) for Li-ion Batteries

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis and Electrochemical Performance of Lithium Rich Cathode Materials xLi₃NbO₄·(1-x)LiMO₂ (M=Mn, Co; 0 ＜ x＜1) for Li-ion Batteries