Citation: Tao-Xiong XIE, Peng-Wen REN, Lin-Yu YU, Wei LI, Hao-Jie DENG, Jian-Bing JIANG. Optimization of Al³⁺ Doping on the Microstructure and Electrochemical Performance of Spinel LiMn₂O₄[J]. Chinese Journal of Structural Chemistry, ;2022, 41(2): 220216. doi: 10.14102/j.cnki.0254-5861.2011-3260 shu

Optimization of Al³⁺ Doping on the Microstructure and Electrochemical Performance of Spinel LiMn₂O₄

College of Packaging and Material Engineering, Hunan University of Technology, Zhuzhou 412007, China

Corresponding author: Jian-Bing JIANG, jjbcsu2011@163.com
Received Date: 20 May 2021
Accepted Date: 30 August 2021

Fund Project: the National Natural Science Foundation of China 51604106Foundation of Hunan Province Department of Education 18C0492Natural Science Foundation of Hunan Province 2019JJ40070the China Postdoctoral Science Foundation 2016M602428

Figures(9)

A series of spinel LiAl_xMn_2-xO₄ (x ≤ 0.1) cathode materials was synthesized by controlled crystallization and solid state route with micro-spherical Mn₃O₄ as the precursor. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to analyze the crystal structure of the synthetic material and the microscopic morphology of the particles. It was found that Al³⁺ doping did not change the spinel structure of the synthesized materials, and the particles had better crystallinity. In the charge and discharge test of the synthesized materials, we found that Al³⁺ doping would slightly reduce the discharge capacity, but it could effectively improve the cyclic stability of the material. The initial capacity of LiAl_0.04Mn_1.96O₄ is 121.6 mAh/g. After 100 cycles at a rate of 1 C (1 C = 148 mA/g), the capacity can still reach 112.9 mAh/g, and the capacity retention rate is 96.4%. Electrochemical impedance spectroscopy (EIS) suggests that Al³⁺ doping can effectively enhance the diffusion capacity of lithium ions in the material.
- micro-spherical Mn₃O₄,
- cyclic stability,
- Al³⁺ doping,
- cathode materials
1. [1]
  Lu, W.; Liang, L.; Sun, X.; Sun, X.; Wu, C.; Hou, L.; Sun, J.; Yuan, C. Recent progresses and development of advanced atomic layer deposition towards high-performance Li-ion batteries. Nanomaterials 2017, 7, 325−28. doi: 10.3390/nano7100325
2. [2]
  Li, Y.; Qi, Z.; Liu, B.; Mclellan, B.; Tang, Y. Substitution effect of new-energy vehicle credit program and corporate average fuel consumption regulation for green-car subsidy. Energy 2018, 152, 223−236. doi: 10.1016/j.energy.2018.03.134
3. [3]
  Jiang, J. B.; Du, K.; Cao, Y. B.; Peng, Z. D.; Hu, G. R.; Duan, J. G. Synthesis of micro-spherical Mn₃O₄ by controlled crystallization method. Powder Technol. 2013, 246, 723−727. doi: 10.1016/j.powtec.2013.04.053
4. [4]
  Tarascon, J. M.; Guyomard, D. The Li_1+xMn₂O₄/C rocking-chair system: a review. Electrochim. Acta 1993, 38, 1221−1231. doi: 10.1016/0013-4686(93)80053-3
5. [5]
  Zhou, W. J.; Bao, S. J.; He, B. L.; Liang, Y. Y.; Li, H. L. Synthesis and electrochemical properties of LiAl_0.05Mn_1.95O₄ by the ultrasonic assisted rheological phase method. Electrochim. Acta 2006, 51, 4701−4708. doi: 10.1016/j.electacta.2006.01.011
6. [6]
  Han, C. G.; Zhu, C. Y.; Saito, G.; Akiyama, T. Improved electrochemical performance of LiMn₂O₄ surface-modified by a Mn⁴⁺-rich phase for rechargeable lithium-ion batteries. Electrochim. Acta 2016, 209, 225−234. doi: 10.1016/j.electacta.2016.05.075
7. [7]
  Lin, B. H.; Yin, Q.; Hu, H. R.; Lu, F. J.; Xia, H. LiMn₂O₄ nanoparticles anchored on graphene nanosheets as high-performance cathode material for lithium-ion batteries. J. Solid State Chem. 2014, 209, 23−28. doi: 10.1016/j.jssc.2013.10.016
8. [8]
  Fergus, J. W. Recent developments in cathode materials for lithium ion batteries. J. Power Sources 2010, 195, 939−954. doi: 10.1016/j.jpowsour.2009.08.089
9. [9]
  Tron, A.; Park, Y. D.; Mun, J. Y. AlF₃-coated LiMn₂O₄ as cathode material for aqueous rechargeable lithium battery with improved cycling stability. J. Power Sources 2016, 325, 360−364. doi: 10.1016/j.jpowsour.2016.06.049
10. [10]
  Xiao, H.; Wang, Y.; Kai, X.; Cheng, S.; Cheng, X. High capacitance LiMn₂O₄ microspheres with different microstructure as cathode material for aqueous asymmetric supercapacitors. J. Alloys Compd. 2017, 738, 25−31.
11. [11]
  Guo, H. J.; Li, X. Q.; He, F. Y.; Li, X. H.; Wang, Z. X.; Peng, W. J. Effects of sodium substitution on properties of LiMn₂O₄ cathode for lithium ion batteries. T. Nonferr. Metal. Soc. 2010, 20, 1043−1048. doi: 10.1016/S1003-6326(09)60255-7
12. [12]
  Kim, H. S.; Na, H. G.; Yang, J. C.; Jung, J. H.; Koo, Y. S.; Hur, N. J.; Kim, H. W. Annealing effects on the structure, photoluminescence, and magnetic properties of GaN/Mn₃O₄ core-shell nanowires. J. Solid State Chem. 2010, 183, 2445−2450. doi: 10.1016/j.jssc.2010.08.006
13. [13]
  Park, J. P.; Kim, S. K.; Park, J. Y.; Hwang, C. H.; Choi, M.; Kim, J. E.; Ok, K. M.; Kwak, H. Y.; Shim, I. W. Syntheses of Mn₃O₄ and LiMn₂O₄ nanoparticles by a simple sonochemical method. Mater. Lett. 2009, 63, 2201−2204. doi: 10.1016/j.matlet.2009.07.027
14. [14]
  Gibot, P.; Laffont, L. Hydrophilic and hydrophobic nano-sized Mn₃O₄ particles. J. Solid State Chem. 2007, 180, 695−701. doi: 10.1016/j.jssc.2006.11.024
15. [15]
  Fang, D. L.; Li, J. C.; Liu, X.; Huang, P. F.; Xu, T. R.; Qian, M. C.; Zheng, C. H. Synthesis of a Co–Ni doped LiMn₂O₄ spinel cathode material for high-power Li-ion batteries by a Sol-gel mediated solid-state route. J. Alloys Compd. 2015, 640, 82−89. doi: 10.1016/j.jallcom.2015.03.243
16. [16]
  Kawai, H.; Nagata, M.; Tukamoto, H.; West, A. R. High-voltage lithium cathode materials. J. Power Sources 1999, 81, 67−72.
17. [17]
  Zhang, H.; Liu, D.; Zhang, X. S.; Zhao, C. J.; Xu, Y. L. Microwave synthesis of LiMg_0.05Mn_1.95O₄ and electrochemical performance at elevated temperature for lithium-ion batteries. J. Solid State Chem. 2013, 18, 569−575.
18. [18]
  Sulochana, A.; Thirunakaran, R.; Sivashanmugam, A.; Gopukumar, S.; Yamaki, J. I. Sol-gel synthesis of 5V LiCu_xMn_2-xO₄ as a cathode material for lithium rechargeable batteries. J. Electrochem. Soc. 2008, 155, A206−A210. doi: 10.1149/1.2828030
19. [19]
  Li, Z.; Lv, X.; Wen, Y.; Fan, W.; Su, H. Carbon combustion synthesis of LiNi_0.5Mn_1.5O₄ and its use as a cathode material for lithium ion batteries. J. Alloys Compd. 2010, 48, 802−805.
20. [20]
  Liu, G. Q.; Wen, L.; Liu, G. Y.; Tian, Y. W. Rate capability of spinel LiCr_0.1Ni_0.4Mn_1.5O₄. J. Alloys Compd. 2010, 501, 233−235. doi: 10.1016/j.jallcom.2010.04.076
21. [21]
  Chen, M. M.; Wu, R. Y.; Ju, S. G.; Zhang, X. X.; Xue, F.; Xing, W. H. Improved performance of Al-doped LiMn₂O₄ ion-sieves for Li⁺ adsorption. Micropor. Mesopor. Mater. 2018, 261, 29−34. doi: 10.1016/j.micromeso.2017.10.058
22. [22]
  Zhan, D.; Liang, Y.; Cui, P.; Xiao, Z. Al-doped LiMn₂O₄ single crystalline nanorods with enhanced elevated-temperature electrochemical performance via a template-engaged method as a cathode material for lithiumion batteries. RSC Adv. 2014, 5, 6372−6377.
23. [23]
  Wang, Y. L.; Wang, W. G; Zhang, Q.; Xin, W.; Cao, J. S.; Shi-Hai, Y. E. Electrochemical performance of Al-doped spinel LiMn₂O₄ cathode material for Li-ion batteries. J. Electrochem. 2013, 19, 232−236.
24. [24]
  Cai, Z.; Ma, Y.; Huang, X.; Yan, X.; Yu, Z.; Zhang, S.; Song, G.; Xu, Y.; Wen, C.; Yang, W. High electrochemical stability Al-doped spinel LiMn₂O₄ cathode material for Li-ion batteries. J. Energy Storage 2020, 27, 101036.1−101036.8.
25. [25]
  Martha, S. K.; Markevich, E.; Burgel, V.; Salitra, G.; Zinigrad, E.; Markovsky, B.; Sclar, H.; Pramovich, Z.; Heik, O.; Aurbach, D.; Exnar, I.; Buqa, H.; Drezen, T.; Semrau, G.; Schmidt, M.; Kovacheva, D.; Saliyski. N. A short review on surface chemical aspects of Li batteries: a key for a good performance. J. Power Sources 2009, 189, 288−296. doi: 10.1016/j.jpowsour.2008.09.084
26. [26]
  Han, D. W.; Ryu, W. H.; Kim, W. K.; Eom, J. Y.; Kwon, H. S. Effects of Li and Cl codoping on the electrochemical performance and structural stability of LiMn₂O₄ cathode materials for hybrid electric vehicle applications. J. Phys. Chem. A 2013, 117, 4913−4919.
27. [27]
  Iturrondobeitia, A.; Goni, A.; Palomares, V.; Muro, I. G.; Lezama, L.; Rojo, T. Effect of doping LiMn₂O₄ spinel with a tetravalent species such as Si(IV) versus with a trivalent species such as Ga(III). Electrochemical, magnetic and ESR study. J. Power Sources 2012, 216, 482−488. doi: 10.1016/j.jpowsour.2012.06.031
28. [28]
  Wang, Y. Z.; Xuan, S.; Xu, H. Y.; Ming, X.; Deng, S. X.; Wang, H.; Liu, J. B.; Yan, H. Facile synthesis of porous LiMn₂O₄ spheres as cathode materials for high-power lithium ion batteries. J. Power Sources 2013, 226, 140−148. doi: 10.1016/j.jpowsour.2012.10.077
1. [1]
  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
2. [2]
  Lingjiang Kou , Yong Wang , Jiajia Song , Taotao Ai , Wenhu Li , Mohammad Yeganeh Ghotbi , Panya Wattanapaphawong , Koji Kajiyoshi . Mini review: Strategies for enhancing stability of high-voltage cathode materials in aqueous zinc-ion batteries. Chinese Chemical Letters, 2025, 36(1): 110368-. doi: 10.1016/j.cclet.2024.110368
3. [3]
  Lumin Zheng , Ying Bai , Chuan Wu . Multi-electron reaction and fast Al ion diffusion of δ-MnO₂ cathode materials in rechargeable aluminum batteries via first-principle calculations. Chinese Chemical Letters, 2024, 35(4): 108589-. doi: 10.1016/j.cclet.2023.108589
4. [4]
  Linping Li , Junhui Su , Yanping Qiu , Yangqin Gao , Ning Li , Lei Ge . Design and fabrication of ternary Au/Co3O4/ZnCdS spherical composite photocatalyst for facilitating efficient photocatalytic hydrogen production. Chinese Journal of Structural Chemistry, 2024, 43(12): 100472-100472. doi: 10.1016/j.cjsc.2024.100472
5. [5]
  Shengyu Zhao , Qinhao Shi , Wuliang Feng , Yang Liu , Xinxin Yang , Xingli Zou , Xionggang Lu , Yufeng Zhao . Suppression of multistep phase transitions of O3-type cathode for sodium-ion batteries. Chinese Chemical Letters, 2024, 35(5): 108606-. doi: 10.1016/j.cclet.2023.108606
6. [6]
  Tao Long , Peng Chen , Bin Feng , Caili Yang , Kairong Wang , Yulei Wang , Can Chen , Yaping Wang , Ruotong Li , Meng Wu , Minhuan Lan , Wei Kong Pang , Jian-Fang Wu , Yuan-Li Ding . Reinforced concrete-like Na_3.5V_1.5Mn_0.5(PO₄)₃@graphene hybrids with hierarchical porosity as durable and high-rate sodium-ion battery cathode. Chinese Chemical Letters, 2024, 35(4): 109267-. doi: 10.1016/j.cclet.2023.109267
7. [7]
  Ruofan Yin , Zhaoxin Guo , Rui Liu , Xian-Sen Tao . Ultrafast synthesis of Na₃V₂(PO₄)₃ cathode for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109643-. doi: 10.1016/j.cclet.2024.109643
8. [8]
  Yuhan Wu , Qing Zhao , Zhijie Wang . Layered vanadium oxides: Promising cathode materials for calcium-ion batteries. Chinese Journal of Structural Chemistry, 2024, 43(5): 100271-100271. doi: 10.1016/j.cjsc.2024.100271
9. [9]
  Runjing Xu , Xin Gao , Ya Chen , Xiaodong Chen , Lifeng Cui . Research status and prospect of rechargeable magnesium ion batteries cathode materials. Chinese Chemical Letters, 2024, 35(11): 109852-. doi: 10.1016/j.cclet.2024.109852
10. [10]
  Husitu Lin , Shuangkun Zhang , Dianfa Zhao , Yongkang Wang , Wei Liu , Fan Yang , Jianjun Liu , Dongpeng Yan , Zhanpeng Wu . Flexible polyphosphazene nanocomposite films: Enhancing stability and luminescence of CsPbBr₃ perovskite nanocrystals. Chinese Chemical Letters, 2025, 36(4): 109795-. doi: 10.1016/j.cclet.2024.109795
11. [11]
  Guangchang Yang , Shenglong Yang , Jinlian Yu , Yishun Xie , Chunlei Tan , Feiyan Lai , Qianqian Jin , Hongqiang Wang , Xiaohui Zhang . Regulating local chemical environment in O3-type layered sodium oxides by dual-site Mg²⁺/B³⁺ substitution achieves durable and high-rate cathode. Chinese Chemical Letters, 2024, 35(9): 109722-. doi: 10.1016/j.cclet.2024.109722
12. [12]
  Mingjiao Lu , Zhixing Wang , Gui Luo , Huajun Guo , Xinhai Li , Guochun Yan , Qihou Li , Xianglin Li , Ding Wang , Jiexi Wang . Boosting the performance of LiNi_0.90Co_0.06Mn_0.04O₂ electrode by uniform Li₃PO₄ coating via atomic layer deposition. Chinese Chemical Letters, 2024, 35(5): 108638-. doi: 10.1016/j.cclet.2023.108638
13. [13]
  Jun Dong , Senyuan Tan , Sunbin Yang , Yalong Jiang , Ruxing Wang , Jian Ao , Zilun Chen , Chaohai Zhang , Qinyou An , Xiaoxing Zhang . Spatial confinement of free-standing graphene sponge enables excellent stability of conversion-type Fe₂O₃ anode for sodium storage. Chinese Chemical Letters, 2025, 36(3): 110010-. doi: 10.1016/j.cclet.2024.110010
14. [14]
  Jing JIN , Zhuming GUO , Zhiyin XIAO , Xiujuan JIANG , Yi HE , Xiaoming LIU . Tuning the stability and cytotoxicity of fac-[Fe(CO)₃I₃]^- anion by its counter ions: From aminiums to inorganic cations. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 991-1004. doi: 10.11862/CJIC.20230458
15. [15]
  Xiping Dong , Xuan Wang , Zhixiu Lu , Qinhao Shi , Zhengyi Yang , Xuan Yu , Wuliang Feng , Xingli Zou , Yang Liu , Yufeng Zhao . Construction of Cu-Zn Co-doped layered materials for sodium-ion batteries with high cycle stability. Chinese Chemical Letters, 2024, 35(5): 108605-. doi: 10.1016/j.cclet.2023.108605
16. [16]
  Shengyu Zhao , Xuan Yu , Yufeng Zhao . A water-stable high-voltage P3-type cathode for sodium-ion batteries. Chinese Chemical Letters, 2024, 35(9): 109933-. doi: 10.1016/j.cclet.2024.109933
17. [17]
  Yue Wang , Caixia Xu , Xingtao Tian , Siyu Wang , Yan Zhao . Challenges and Modification Strategies of High-Voltage Cathode Materials for Li-ion Batteries. Chinese Journal of Structural Chemistry, 2023, 42(10): 100167-100167. doi: 10.1016/j.cjsc.2023.100167
18. [18]
  Na Li , Wenxue Wang , Peng Wang , Zhanying Sun , Xinlong Tian , Xiaodong Shi . Dual-defect engineering of catalytic cathode materials for advanced lithium-sulfur batteries. Chinese Chemical Letters, 2025, 36(3): 110731-. doi: 10.1016/j.cclet.2024.110731
19. [19]
  Fan Wu , Shaoyang Wu , Xin Ye , Yurong Ren , Peng Wei . Research progress of high-entropy cathode materials for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(4): 109851-. doi: 10.1016/j.cclet.2024.109851
20. [20]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(305)
HTML views(5)

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

Optimization of Al3+ Doping on the Microstructure and Electrochemical Performance of Spinel LiMn2O4

Metrics

通讯作者: 陈斌, bchen63@163.com

Optimization of Al³⁺ Doping on the Microstructure and Electrochemical Performance of Spinel LiMn₂O₄