Citation: Ding Feixiang, Gao Fei, Rong Xiaohui, Yang Kai, Lu Yaxiang, Hu Yong-Sheng. Mixed-Phase Na_0.65Li_0.13Mg_0.13Ti_0.74O₂ as a High-Performance Na-Ion Battery Layered Anode[J]. Acta Physico-Chimica Sinica, ;2020, 36(5): 190402. doi: 10.3866/PKU.WHXB201904022 shu

Mixed-Phase Na_0.65Li_0.13Mg_0.13Ti_0.74O₂ as a High-Performance Na-Ion Battery Layered Anode

Ding Feixiang ^1,2,† ,
Gao Fei ^1,† ,
Rong Xiaohui ^1,2 ,
Yang Kai ¹ ,
Lu Yaxiang ² ,
Hu Yong-Sheng ^2,,

1.
State Key Laboratory of Operation and Control of Renewable Energy & Storage Systems, China Electric Power Research Institute, Beijing 100192, P. R. China
2.
Institute of Physics, Chinese Academy of Sciences, Beijing 100190, P. R. China

Corresponding author: Hu Yong-Sheng, yshu@iphy.ac.cn

^†

Received Date: 4 April 2019
Revised Date: 28 April 2019
Accepted Date: 14 May 2019
Available Online: 31 May 2019

With the development of clean and sustainable energy sources, the demand for large-scale electrochemical energy storage systems has rapidly increased over the last few years. Rechargeable Na-ion batteries (NIBs), one of the most promising energy storage technologies, have received a great deal of attention. Titanium-based P2-type layered oxides are attractive candidates for NIB anode materials, owing to their suitable redox potential, low cost, air stability and high safety. The exposed large interlayers of P2 configuration provide facile channels for Na⁺ insertion/extraction when employed as electrode materials for room temperature, non-aqueous NIBs. In this paper, a novel P2-type Na_0.65Li_0.13Mg_0.13Ti_0.74O₂ is synthesized by a solid-state reaction method. An orthorhombic phase of Na_0.9Mg_0.45Ti_1.55O₂ is observed with the increase in calcination time. During the long calcination process, it is speculated that some lattice Na⁺ and Li⁺ of the previously formed P2 phase compound would be volatilized or extracted by O₂, forming a low Na-content orthorhombic phase based on the layered host structure. In particular, when the precursor was calcined at 1273 K for 24 h, a perfect biphasic hybrid composite was synthesized. The Na storage performance of the pure P2 compound and hybrid composite were evaluated respectively in sodium half cells with voltage range of 0.2–2.5 V. The P2-type electrode can deliver a reversible capacity of 85.1 mAh·g^-1 (theoretical capacity of approximately 108.5 mAh·g^-1), whereas, the sample with the orthorhombic phase shows an enhanced initial reversible capacity of 96.3 mAh·g^-1. Both of the curves are smooth with no observed plateau, indicating the good structural stability of the electrode during cycling. Thus, the hybrid composite exhibits better cycling performance (capacity retention of 89.7% vs. 84.4% for pure P2, after 400 cycles at current density of 1C) and better rate capability (56.6 mAh·g^-1 at 5C vs 47.1 mAh·g^-1 at 2C). These results can be attributed to the introduced second phase, which improves the electron and bulk ion conductivity and helps stabilize the structure. Therefore, this novel two-phase intergrowth composite could serve as a promising anode candidate for the large-scale energy storage application of NIBs. Moreover, this structural design strategy could be used for other layered oxides to improve their energy density and cycling stability.
- Na-ion battery,
- P2-type layered structure,
- Anode material,
- Second phase,
- High reversible capacity
1. [1]
  Ding, F.; Li, J.; Deng, F.; Xu, G.; Liu, Y.; Yang, K.; Kang, F. ACS Appl. Mater. Interfaces 2017, 9, 27936. doi: 10.1021/acsami.7b07221 doi: 10.1021/acsami.7b07221
2. [2]
  Li, M.; Lu, J.; Chen, Z.; Amine, K. Adv. Mater. 2018, 1800561. doi: 10.1002/adma.201800561 doi: 10.1002/adma.201800561
3. [3]
  Pan, H.; Hu, Y. S.; Chen, L. Energy Environ. Sci. 2013, 6, 2338. doi:10.1039/c3ee40847g doi: 10.1039/c3ee40847g
4. [4]
  Lu, Y.; Zhao, C.; Qi, X.; Qi, Y.; Li, H.; Huang, X.; Chen, L.; Hu, Y. S. Adv. Energy Mater. 2018, 8, 1800108. doi: 10.1002/aenm.201800108 doi: 10.1002/aenm.201800108
5. [5]
  Zhao, C.; Wang, Q.; Lu, Y.; Li, B.; Chen, L.; Hu, Y. S. Sci. Bull. 2018, 63, 1125. doi: 10.1016/j.scib.2018.07.018 doi: 10.1016/j.scib.2018.07.018
6. [6]
  Qi, Y.; Mu, L.; Zhao, J.; Hu, Y. S.; Liu, H.; Dai, S. Angew. Chem. Int. Ed. 2015, 54, 9911. doi: 10.1002/anie.201503188 doi: 10.1002/anie.201503188
7. [7]
  Qi, Y.; Zhao, J.; Yang, C.; Liu, H.; Hu, Y. S. Small Methods 2018, 1800111. doi: 10.1002/smtd.201800111 doi: 10.1002/smtd.201800111
8. [8]
  Li, Q.; Jiang, K.; Li, X.; Qiao, Y.; Zhang, X.; He, P.; Guo, S.; Zhou, H. Adv. Energy Mater. 2018, 8. doi: 10.1002/aenm.201801162 doi: 10.1002/aenm.201801162
9. [9]
  Hwang, J. Y.; Myung, S. T.; Sun, Y. K. Chem. Soc. Rev. 2017, 46, 3529. doi: 10.1039/c6cs00776g doi: 10.1039/c6cs00776g
10. [10]
  Wang, Y.; Yu, X.; Xu, S.; Bai, J.; Xiao, R.; Hu, Y. S.; Li, H.; Yang, X. Q.; Chen, L.; Huang, X. Nat. Commun. 2013, 4, 2365. doi: 10.1038/ncomms3365 doi: 10.1038/ncomms3365
11. [11]
  Wang, P. F.; Yao, H. R.; Zuo, T. T.; Yin, Y. X.; Guo, Y. G. Chem. Commun. 2017, 53, 1957. doi: 10.1039/c6cc09378g doi: 10.1039/c6cc09378g
12. [12]
  Wang, Y.; Xiao, R.; Hu, Y. S.; Avdeev, M.; Chen, L. Nat. Commun. 2015, 6, 6954. doi: 10.1038/ncomms7954 doi: 10.1038/ncomms7954
13. [13]
  Yu, H.; Ren, Y.; Xiao, D.; Guo, S.; Zhu, Y.; Qian, Y.; Gu, L.; Zhou, H. Angew. Chem. Int. Ed. 2014, 53, 8963. doi: 10.1002/anie.201404549 doi: 10.1002/anie.201404549
14. [14]
  Zhao, C.; Avdeev, M.; Chen, L.; Hu, Y. S. Angew. Chem. Int. Ed. 2018, 57, 7056. doi: 10.1002/anie.201801923 doi: 10.1002/anie.201801923
15. [15]
  Wang, P. F.; You, Y.; Yin, Y. X.; Wang, Y. S.; Wan, L. J.; Gu, L.; Guo, Y. G. Angew. Chem. Int. Ed. 2016, 55, 7445. doi: 10.1002/anie.201602202 doi: 10.1002/anie.201602202
16. [16]
  Zhao, W.; Tsuchiya, Y.; Yabuuchi, N. Small Methods 2018, 1800032. doi: 10.1002/smtd.201800032 doi: 10.1002/smtd.201800032
17. [17]
  Chen, J.; Li, L.; Wu, L.; Yao, Q.; Yang, H.; Liu, Z.; Xia, L.; Chen, Z.; Duan, J.; Zhong, S. J. Power Sources 2018, 406, 110. doi: 10.1016/j.jpowsour.2018.10.058 doi: 10.1016/j.jpowsour.2018.10.058
18. [18]
  Yabuuchi, N.; Hara, R.; Kajiyama, M.; Kubota, K.; Ishigaki, T.; Hoshikawa, A.; Komaba, S. Adv. Energy Mater. 2014, 4, 1301453. doi: 10.1002/aenm.201301453 doi: 10.1002/aenm.201301453
19. [19]
  Li, Z.; Ding, F.; Zhao, Y.; Wang, Y.; Li, J.; Yang, K.; Gao, F. Ceram. Inter. 2016, 42, 15464. doi: 10.1016/j.ceramint.2016.06.198 doi: 10.1016/j.ceramint.2016.06.198
20. [20]
  Guo, S.; Yu, H.; Liu, P.; Ren, Y.; Zhang, T.; Chen, M.; Ishida, M.; Zhou, H. Energy Environ. Sci. 2015, 8, 1237. doi: 10.1039/c4ee03361b doi: 10.1039/c4ee03361b
21. [21]
  Guo, S.; Liu, P.; Sun, Y.; Zhu, K.; Yi, J.; Chen, M.; Ishida, M.; Zhou, H. Angew. Chem. Int. Ed. 2015, 54, 11701. doi: 10.1002/anie.201505215 doi: 10.1002/anie.201505215
22. [22]
  Xiao, Y.; Wang, P. F.; Yin, Y. X.; Zhu, Y. F.; Yang, X.; Zhang, X. D.; Wang, Y.; Guo, X. D.; Zhong, B. H.; Guo, Y. G. Adv. Energy Mater. 2018, 8, 1800492. doi: 10.1002/aenm.201800492 doi: 10.1002/aenm.201800492
1. [1]
  Shan Zhao , Xu Liu , Haotian Guo , Zonglin Liu , Pengfei Wang , Jie Shu , Tingfeng Yi . Synergistic design of high-entropy P2/O3 biphasic cathodes for high-performance sodium-ion batteries. Acta Physico-Chimica Sinica, 2026, 42(1): 100129-0. doi: 10.1016/j.actphy.2025.100129
2. [2]
  Yu Guo , Zhiwei Huang , Yuqing Hu , Junzhe Li , Jie Xu . Recent Advances in Iron-based Heterostructure Anode Materials for Sodium Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(3): 100022-0. doi: 10.3866/PKU.WHXB202311015
3. [3]
  Li Peicai , Wang Xubin , Zhang Qinghua , Wang Bowen , Rong Xiaohui , Hu Yong-Sheng , Li Zhongtao . High-rate and long-cycling P2-type cathode material for sodium-ion batteries. Acta Physico-Chimica Sinica, 2026, 42(5): 100214-. doi: 10.1016/j.actphy.2025.100214
4. [4]
  Rongzhan LOU , Qiaoling KANG , Zhenchao BAI , Dongyun LI , Yang XU , Rui WANG , Qingyi LU . Research progress of sodium ion high entropy layered oxide cathode. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2411-2428. doi: 10.11862/CJIC.20250142
5. [5]
  Zhuo WANG , Xiaotong LI , Zhipeng HU , Junqiao PAN . Three-dimensional porous carbon decorated with nano bismuth particles: Preparation and sodium storage properties. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 267-274. doi: 10.11862/CJIC.20240223
6. [6]
  Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang . Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100035-0. doi: 10.3866/PKU.WHXB202406014
7. [7]
  Zilin Hu , Yaoshen Niu , Xiaohui Rong , Yongsheng Hu . Suppression of Voltage Decay through Ni³⁺ Barrier in Anionic-Redox Active Cathode for Na-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(6): 2306005-0. doi: 10.3866/PKU.WHXB202306005
8. [8]
  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): 2407023-0. doi: 10.3866/PKU.WHXB202407023
9. [9]
  Qiang Huang , Yue Wang , Xuejie Wang , Lyubov G. Bulusheva , Tao Liu . La-Ce双掺杂调控电子结构及离子传输增强Na₄Fe₃(PO₄)₂P₂O₇正极的超快储钠性能. Acta Physico-Chimica Sinica, 2026, 42(11): 100339-. doi: 10.1016/j.actphy.2026.100339
10. [10]
  Ziying YUAN , Zhen DUAN , Dan LIU , Jingrui NIU , Feiyan LAI , Xiaohui ZHANG , Guangchang YANG . Modification of O3-type Na_0.86Ni_1/3Fe_1/3Mn_1/3O₂ cathode material via Ti⁴⁺/P⁵⁺ dual-site co-doping. Chinese Journal of Inorganic Chemistry, 2026, 42(8): 1647-1657. doi: 10.11862/CJIC.20260041
11. [11]
  Xueyu Lin , Ruiqi Wang , Wujie Dong , Fuqiang Huang . Rational Design of Bimetallic Oxide Anodes for Superior Li⁺ Storage. Acta Physico-Chimica Sinica, 2025, 41(3): 100021-0. doi: 10.3866/PKU.WHXB202311005
12. [12]
  Wenhui Li , Yakun Tang , Yusheng Zhou , Yue Zhang , Wenhai Zhang , Qingtao Ma , Lang Liu , Sen Dong , Yuliang Cao . Enhanced sodium storage performance of asphalt-derived hard carbon through intramolecular oxidation for high-performance sodium-ion batteries. Acta Physico-Chimica Sinica, 2025, 41(10): 100119-0. doi: 10.1016/j.actphy.2025.100119
13. [13]
  Xue Xiao , Jiachun Li , Xiangtong Meng , Jieshan Qiu . Sulfur-Doped Carbon-Coated Fe_0.95S_1.05 Nanospheres as Anodes for High-Performance Sodium Storage. Acta Physico-Chimica Sinica, 2024, 40(6): 2307006-0. doi: 10.3866/PKU.WHXB202307006
14. [14]
  Débora Ferreira dos Santos Morais , José Luis Tirado , Carlos Pérez-Vicente , Fabiana Villela da Motta , Pedro Lavela , Mauricio Bomio , Sergio Lavela . Unlocking the performance of sodium-ion batteries by coating Na₃V₂(PO₄)₃ with Nb₂O₅. Acta Physico-Chimica Sinica, 2026, 42(2): 100180-0. doi: 10.1016/j.actphy.2025.100180
15. [15]
  Zhicheng JU , Wenxuan FU , Baoyan WANG , Ao LUO , Jiangmin JIANG , Yueli SHI , Yongli CUI . MOF-derived nickel-cobalt bimetallic sulfide microspheres coated by carbon: Preparation and long cycling performance for sodium storage. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 661-674. doi: 10.11862/CJIC.20240363
16. [16]
  Xiaotian ZHU , Fangding HUANG , Wenchang ZHU , Jianqing ZHAO . Layered oxide cathode for sodium-ion batteries: Surface and interface modification and suppressed gas generation effect. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 254-266. doi: 10.11862/CJIC.20240260
17. [17]
  Fan Yang , Zheng Liu , Da Wang , KwunNam Hui , Yelong Zhang , Zhangquan Peng . Preparation and Properties of P-Bi₂Te₃/MXene Superstructure-based Anode for Potassium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2303006-0. doi: 10.3866/PKU.WHXB202303006
18. [18]
  Zhang Xue , He Zihan , Wu Yingqi , Yu Weilai , Liu Tao . Corn-distillers-derived hard carbon: a sustainable high-rate, long-life anode for sodium-ion batteries. Acta Physico-Chimica Sinica, 2026, 42(5): 100199-. doi: 10.1016/j.actphy.2025.100199
19. [19]
  Wang Shuang , Fu Xiaoqi , Yao Shanshan . Synergistic optimization of ion migration and electron transfer in sodium-ion battery cathode materials. Acta Physico-Chimica Sinica, 2026, 42(5): 100206-. doi: 10.1016/j.actphy.2025.100206
20. [20]
  Mingyuan Pang , Yiping Su , Haohao Zhang , Laixin Hong , Yue Wang , Yujie Ma , Min Yang , Mengge Guo , Zimai Wang , Zhen Kong , Jiajia Ye , Juan An , Guanglei Wu . Bi₂S₃@Sn_0.904O₂中硫空位与锡空位的协同构筑及其作为长寿命锂离子电池负极材料. Acta Physico-Chimica Sinica, 2026, 42(11): 100368-. doi: 10.1016/j.actphy.2026.100368

Get Citation

PDF

XML

Metrics

PDF Downloads(21)
Abstract views(2451)
HTML views(238)

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

Mixed-Phase Na0.65Li0.13Mg0.13Ti0.74O2 as a High-Performance Na-Ion Battery Layered Anode

Metrics

通讯作者: 陈斌, bchen63@163.com

Mixed-Phase Na_0.65Li_0.13Mg_0.13Ti_0.74O₂ as a High-Performance Na-Ion Battery Layered Anode