高性能三元NASICON型Na3.5−xMn0.5V1.5−xZrx(PO4)3/C钠离子电池正极材料

doi:10.3866/PKU.WHXB202407023

Abstract

Abstract:

Sodium-ion batteries (SIBs) are widely studied for energy storage applications, but achieving cathode materials with balanced high energy density, stability, and fast charge/discharge performance remains a key challenge. In this study, we successfully synthesized a series of NASICON-type Na_3.5−xMn_0.5V_1.5−xZr_x(PO₄)₃/C, incorporating Mn, V, and Zr to investigate their impact on electrochemical performance. By introducing Zr alongside Mn and V, we developed a novel strategy to activate V⁴⁺/V⁵⁺ redox reactions, achieving high energy density. Moreover, this substitution promotes Na-ion migration by widening the migration pathways and generating additional Na vacancies, which greatly enhances electrode reaction kinetics and boosts overall performance. Na_3.4Mn_0.5V_1.4Zr_0.1(PO₄)₃/C demonstrates superior stability, retaining 90% of its capacity after 800 cycles, and delivers high-rate performance (84 mAh∙g⁻¹ at 20C), significantly outperforming pristine Na_3.5Mn_0.5V_1.5(PO₄)₃/C. These advancements highlight a potential approach for developing efficient and sustainable SIBs.

Key words: Sodium-ion batteries, NASICON, Cathode materials, Cycling stability, Rate capability

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[J]. Acta Phys. -Chim. Sin. 2024, 40(12), 2407023. doi: 10.3866/PKU.WHXB202407023

Figures/Tables 5

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

References 52

1	Armand M. ; Tarascon J.-M Nature 2008, 451, 652. doi: 10.1038/451652a
2	Davies D. M. ; Verde M. G. ; Mnyshenko O. ; Chen Y. R. ; Rajeev R. ; Meng Y. S. ; Elliott G Nat. Energy 2018, 4, 42. doi: 10.1038/s41560-018-0290-1
3	Hu Z. ; Niu Y. ; Rong X. ; Hu Y Acta Phys.-Chim. Sin. 2024, 40, 2306005.
	胡紫霖; 牛耀申; 容晓晖; 胡勇胜. 物理化学学报, 2024, 40, 2306005. doi: 10.3866/pku.Whxb202306005
4	Yu H. ; Ruan X. ; Wang J. ; Gu Z. ; Liang Q. ; Cao J.-M. ; Kang J. ; Du C.-F. ; Wu X.-L. ACS Nano 2022, 16, 21174. doi: 10.1021/acsnano.2c09122
5	Song C. ; Li S. ; Bai Y Nano Res. 2023, 17, 2728. doi: 10.1007/s12274-023-6164-2
6	Chen M. ; Hua W. ; Xiao J. ; Zhang J. ; Lau V. W.-H. ; Park M. ; Lee G.-H. ; Lee S. ; Wang W. ; Peng J. ; et al J. Am. Chem. Soc. 2021, 143, 18091. doi: 10.1021/jacs.1c06727
7	Wang K. ; Li H. ; Guo G. ; Zheng L. ; Passerini S. ; Zhang H ACS Energy Lett. 2023, 8, 1671. doi: 10.1021/acsenergylett.2c02837
8	Heng Y. ; Gu Z. ; Guo J. ; Wu X Acta Phys.-Chim. Sin. 2021, 37, 2005013.
	衡永丽; 谷振一; 郭晋芝; 吴兴隆. 物理化学学报, 2021, 37, 2005013. doi: 10.3866/PKU.WHXB202005013
9	Ahsan Z. ; Cai Z. ; Wang S. ; Moin M. ; Wang H. ; Liu D. ; Ma Y. ; Song G. ; Wen C Adv. Energy Mater. 2024, 14, 2400373. doi: 10.1002/aenm.202400373
10	Sun L. ; Wu Z. ; Hou M. ; Ni Y. ; Sun H. ; Jiao P. ; Li H. ; Zhang W. ; Zhang L. ; Zhang K. ; et al Energy Environ. Sci 2024, 17, 210. doi: 10.1039/d3ee02817h
11	Buryak N. S. ; Anishchenko D. V. ; Levin E. E. ; Ryazantsev S. V. ; Martin-Diaconescu V. ; Zakharkin M. V. ; Nikitina V. A. ; Antipov E. V J. Power Sources 2022, 518, 230769. doi: 10.1016/j.jpowsour.2021.230769
12	Xu C. ; Zhao J. ; Wang Y.-A. ; Hua W. ; Fu Q. ; Liang X. ; Rong X. ; Zhang Q. ; Guo X. ; Yang C. ; et al Adv. Energy Mater. 2022, 12, 2200966. doi: 10.1002/aenm.202200966
13	Shao Y. ; Qian Y. ; Zhang T. ; Zhang P. ; Wang H. ; Qian T. ; Yan C Inorg. Chem. Front. 2024, 11, 4552. doi: 10.1039/d4qi01141d
14	Meng W. ; Dang Z. ; Li D. ; Jiang L Adv. Mater. 2023, 35, 2301376. doi: 10.1002/adma.202301376
15	Gao H. ; Seymour I. D. ; Xin S. ; Xue L. ; Henkelman G. ; Goodenough J. B J. Am. Chem. Soc 2018, 140, 18192. doi: 10.1021/jacs.8b11388
16	Tian J.-L. ; Wu L.-R. ; Zhao H.-J. ; Xu S.-D. ; Chen L. ; Zhang D. ; Duan X.-C. Rare Met. 2023, 43, 113. doi: 10.1007/s12598-023-02422-w
17	Chu S. ; Guo S. ; Zhou H Chem. Soc. Rev 2021, 50, 13189. doi: 10.1039/d1cs00442e
18	Cao X. ; Zhou J. ; Pan A. ; Liang S Acta Phys.-Chim. Sin. 2020, 36, 1905018.
	曹鑫鑫; 周江; 潘安强; 梁叔全. 物理化学学报, 1905, 36, 1905018. doi: 10.3866/PKU.WHXB201905018
19	Hu P. ; Zou Z. ; Sun X. ; Wang D. ; Ma J. ; Kong Q. ; Xiao D. ; Gu L. ; Zhou X. ; Zhao J. ; et al Adv. Mater. 2020, 32, 1907526. doi: 10.1002/adma.201907526
20	Li B. ; Xiao D. ; Shang C. ; Wang X. ; Yan M. ; Hu P J. Alloy. Compd. 2024, 977, 173259. doi: 10.1016/j.jallcom.2023.173259
21	Ge X. ; He L. ; Guan C. ; Wang X. ; Li J. ; Lai Y. ; Zhang Z ACS Nano 2023, 18, 1714. doi: 10.1021/acsnano.3c10319
22	Li Y. ; Chen B. ; Wang Y. ; Xing H. ; Zhao W. ; Zhang G. ; Shi S Acta Phys.-Chim. Sin. 2024, 40, 2305053.
	李亚捷; 陈斌; 王依平; 邢辉; 赵伟; 张更; 施思齐. 物理化学学报, 2024, 40, 2305053. doi: 10.3866/PKU.WHXB202305053
23	Hou J. ; Hadouchi M. ; Sui L. ; Liu J. ; Tang M. ; Hay Kan W. ; Avdeev M. ; Zhong G. ; Liao Y. ; Lai Y. ; et al Energy Storage Mater. 2021, 42, 307. doi: 10.1016/j.ensm.2021.07.040
24	Singh B. ; Wang Z. ; Park S. ; Gautam G. S. ; Chotard J.-N. ; Croguennec L. ; Carlier D. ; Cheetham A. K. ; Masquelier C. ; Canepa P J. Mater. Chem. A 2021, 9, 281. doi: 10.1039/d0ta10688g
25	Snarskis G. ; Pilipavičius J. ; Gryaznov D. ; Mikoliu̅naitė L. ; Vilčiauskas L Chem. Mater 2021, 33, 8394. doi: 10.1021/acs.chemmater.1c02775
26	Huang H.-B. ; Luo S.-H. ; Liu C.-L. ; Yang Y. ; Zhai Y.-C. ; Chang L.-J. ; Li M.-Q. Appl. Surf. Sci. 2019, 487, 1159. doi: 10.1016/j.apsusc.2019.05.224
27	Li H. ; Wang Y. ; Zhao X. ; Jin J. ; Shen Q. ; Li J. ; Liu Y. ; Qu X. ; Jiao L. ; Liu Y ACS Energy Lett. 2023, 8, 3666. doi: 10.1021/acsenergylett.3c01183
28	Qiao S. ; Zhou Q. ; Ma M. ; Liu H. ; Dou S. ; Chong S ACS Nano 2023, 17, 11220. doi: 10.1021/acsnano.3c02892
29	Zhao Y. ; Liu Q. ; Zhao X. ; Mu D. ; Tan G. ; Li L. ; Chen R. ; Wu F Mater. Today 2023, 62, 271. doi: 10.1016/j.mattod.2022.11.024
30	Guo J. Z. ; Zhang H. X. ; Gu Z. Y. ; Du M. ; Lu H. Y. ; Zhao X. X. ; Yang J. L. ; Li W. H. ; Kang S. ; Zou W. ; et al Adv. Funct. Mater. 2022, 32, 2209482. doi: 10.1002/adfm.202209482
31	Li B. ; Mei J. ; Wang X. ; Shang C. ; Shen X. ; Hu P Energy Fuels 2024, 38, 1508. doi: 10.1021/acs.energyfuels.3c03740
32	Li B. ; Zou Y. ; Zhang S. ; Xiao D. ; Shang C. ; Wang X. ; Yan M. ; Hu P Electrochim. Acta 2024, 475, 143666. doi: 10.1016/j.electacta.2023.143666
33	Kabbour H. ; Coillot D. ; Colmont M. ; Masquelier C. ; Mentré O J. Am. Chem. Soc 2011, 133, 11900. doi: 10.1021/ja204321y
34	Geng Y. ; Zhang T. ; Xu T. ; Mao W. ; Li D. ; Dai K. ; Zhang J. ; Ai G Energy Storage Mater. 2022, 49, 67. doi: 10.1016/j.ensm.2022.03.044
35	Nagai T. ; Mochizuki Y. ; Yoshida S. ; Kimura T J. Am. Chem. Soc 2023, 145, 8090. doi: 10.1021/jacs.3c00797
36	Wang S.-M. ; Li J.-Q. ; Xu L. ; Sun M.-J. ; Huang W.-J. ; Liu Q. ; Ren F.-T. ; Sun Y.-J. ; Duan L.-Y. ; Ma H. ; et al Rare Met. 2024, 43, 4253. doi: 10.1007/s12598-024-02777-8
37	Difi S. ; Saadoune I. ; Sougrati M. T. ; Hakkou R. ; Edstrom K. ; Lippens P.-E. J. Phys. Chem. C 2015, 119, 25220. doi: 10.1021/acs.jpcc.5b07931
38	Xu L. ; Li J. ; Liu C. ; Zou G. ; Hou H. ; Ji X Acta Phys.-Chim. Sin. 2020, 36, 1905013.
	徐来强; 李佳阳; 刘城; 邹国强; 侯红帅; 纪效波. 物理化学学报, 1905, 36, 1905013. doi: 10.3866/PKU.WHXB201905013
39	Liu X. ; Feng G. ; Wu Z. ; Wang D. ; Wu C. ; Yang L. ; Xiang W. ; Chen Y. ; Guo X. ; Zhong B J. Alloy. Compd. 2020, 815, 152430. doi: 10.1016/j.jallcom.2019.152430
40	Guo J.-Z. ; Gu Z.-Y. ; Du M. ; Zhao X.-X. ; Wang X.-T. ; Wu X.-L. Mater. Today 2023, 66, 221. doi: 10.1016/j.mattod.2023.03.020
41	Liu Y. ; Rong X. ; Bai R. ; Xiao R. ; Xu C. ; Zhang C. ; Xu J. ; Yin W. ; Zhang Q. ; Liang X. ; et al Nat. Energy 2023, 8, 1088. doi: 10.1038/s41560-023-01301-z
42	Qin D. ; Ding J. ; Liang C. ; Liu Q. ; Feng L. ; Luo Y. ; Hu G. ; Luo J. ; Liu X Acta Phys.-Chim. Sin. 2024, 40, 2310034.
	秦豆豆; 丁俊阳; 梁初; 刘倩; 冯立纲; 罗扬; 胡广志; 罗俊; 刘熙俊. 物理化学学报, 2024, 40, 2310034. doi: 10.3866/pku.Whxb202310034
43	Liu Y. ; Zhou Y. ; Zhang J. ; Xia Y. ; Chen T. ; Zhang S ACS Sustain. Chem. Eng. 2016, 5, 1306. doi: 10.1021/acssuschemeng.6b01536
44	Qi X.-R. ; Liu Y. ; Ma L.-L. ; Hou B.-X. ; Zhang H.-W. ; Li X.-H. ; Wang Y.-S. ; Hui Y.-Q. ; Wang R.-X. ; Bai C.-Y. ; et al Rare Met. 2022, 41, 1637. doi: 10.1007/s12598-021-01900-3
45	Pan W. ; Guan W. ; Jiang Y Acta Phys.-Chim. Sin. 2020, 36, 1905017.
	潘雯丽; 关文浩; 姜银珠. 物理化学学报, 2020, 36, 1905017. doi: 10.3866/PKU.WHXB201905017
46	Wang D. ; Yin X. ; Wu J. ; Luo Y. ; Shi S Acta Phys.-Chim. Sin. 2024, 40, 2307029.
	王达; 殷晓彬; 吴剑芳; 罗亚桥; 施思齐. 物理化学学报, 2307, 40, 2307029. doi: 10.3866/pku.Whxb202307029
47	Tang A. ; Zhang S. ; Lin W. ; Xiao D. ; Ma J. ; Shang C. ; Yan M. ; Zhang Z. ; Chen C. ; Huang Z. ; et al Energy Storage Mater. 2023, 58, 271. doi: 10.1016/j.ensm.2023.03.024
48	Zhou W. ; Xue L. ; Lü X. ; Gao H. ; Li Y. ; Xin S. ; Fu G. ; Cui Z. ; Zhu Y. ; Goodenough J. B Nano Lett. 2016, 16, 7836. doi: 10.1021/acs.nanolett.6b04044
49	Anishchenko D. V. ; Zakharkin M. V. ; Nikitina V. A. ; Stevenson K. J. ; Antipov E. V Electrochim. Acta 2020, 354, 136761. doi: 10.1016/j.electacta.2020.136761
50	Zhang J. ; Zhao X. ; Song Y. ; Li Q. ; Liu Y. ; Chen J. ; Xing X Energy Storage Mater. 2019, 23, 25. doi: 10.1016/j.ensm.2019.05.041
51	Fu Y. ; Zhu C Acta Phys.-Chim. Sin. 2023, 39, 2209002.
	傅焰鹏; 朱昌宝. 物理化学学报, 2209, 39, 2209002. doi: 10.3866/PKU.WHXB202209002
52	Han Y. ; Wang X. ; Yan W. ; Buzlukov A. L. ; Hu P. ; Zhang L. ; Yu J. ; Liu T ACS Appl. Mater. Interfaces 2024, 16, 35114. doi: 10.1021/acsami.4c05943

[1]	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 [J]. Acta Phys. -Chim. Sin., 2026, 42(2): 100180-.
[2]	Liangliang Song, Haoyan Liang, Shunqing Li, Bao Qiu, Zhaoping Liu. Challenges and strategies on high-manganese Li-rich layered oxide cathodes for ultrahigh-energy-density batteries [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100085-.
[3]	Ying Li, Yushen Zhao, Kai Chen, Xu Liu, Tingfeng Yi, Li-Feng Chen. Rational Design of Cross-Linked N-Doped C-Sn Nanofibers as Free-Standing Electrodes towards High-Performance Li-Ion Battery Anodes [J]. Acta Phys. -Chim. Sin., 2024, 40(3): 2305007-.
[4]	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 [J]. Acta Phys. -Chim. Sin., 2024, 40(10): 2310034-.
[5]	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.
[6]	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.
[7]	Kuangyu Wang, Kai Liu, Hui Wu. Molten Alkali Metal Batteries Based on Solid Electrolytes [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2301009-.
[8]	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-.
[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]	Wenli Pan,Wenhao Guan,Yinzhu Jiang. Research Advances in Polyanion-Type Cathodes for Sodium-Ion Batteries [J]. Acta Physico-Chimica Sinica, 2020, 36(5): 1905017-.
[12]	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.
[13]	Jiangtao HU, Jiaxin ZHENG, Feng PAN. Research Progress into the Structure and Performance of LiFePO₄ Cathode Materials [J]. Acta Physico-Chimica Sinica, 2019, 35(4): 361-370.
[14]	Lei. HE,Jun-Min. XU,Yong-Jian. WANG,Chang-Jin. ZHANG. LiFePO₄-Coated Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ as Cathode Materials with High Coulombic Efficiency and Improved Cyclability for Li-Ion Batteries [J]. Acta Phys. -Chim. Sin., 2017, 33(8): 1605-1613.
[15]	ZHANG Yuan-Hang, WANG Zhi-Yuan, SHI Chun-Sheng, LIU En-Zuo, HE Chun-Nian, ZHAO Nai-Qin. Synthesis of Uniform Nickel Oxide Nanoparticles Embedded in Porous Hard Carbon Spheres and Their Application in High Performance Li-Ion Battery Anode Materials [J]. Acta Phys. -Chim. Sin., 2015, 31(2): 268-276.

Enhanced Performance of Ternary NASICON-Type Na_3.5−xMn_0.5V_1.5−xZr_x (PO₄)₃/C Cathodes for Sodium-Ion Batteries

RichHTML

Full text @ ScienceDirect

Like

Supplement

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 52

Related Articles 15

Metrics

Recommended 0

Enhanced Performance of Ternary NASICON-Type Na3.5−xMn0.5V1.5−xZrx (PO4)3/C Cathodes for Sodium-Ion Batteries

RichHTML

Full text @ ScienceDirect

Like

Supplement

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 5

References 52

Related Articles 15

Metrics

Recommended 0

Enhanced Performance of Ternary NASICON-Type Na_3.5−xMn_0.5V_1.5−xZr_x (PO₄)₃/C Cathodes for Sodium-Ion Batteries