Al掺杂P2型Na0.8Ni0.33Mn0.67-xAlxO2钠离子电池正极材料的制备与电化学性能

doi:10.15541/jim20240499

无机材料学报 ›› 2025, Vol. 40 ›› Issue (9): 1005-1012.DOI: 10.15541/jim20240499

Al掺杂P2型Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂钠离子电池正极材料的制备与电化学性能

闫共芹¹^,²(), 王晨¹, 蓝春波¹^,², 洪雨昕¹, 叶维超¹, 付向辉¹

1.广西科技大学机械与汽车工程学院, 柳州 545616
2.广西汽车零部件与整车技术重点实验室, 柳州 545616

收稿日期:2024-12-02 修回日期:2025-02-03 出版日期:2025-09-20 网络出版日期:2025-03-06
作者简介:闫共芹(1982-), 男, 副教授. E-mail: ygq@gxust.edu.cn
基金资助:
广西壮族自治区自然科学基金(2020GXNSFAA159024);广西高校中青年教师科研基础能力提升项目(2022KY0350);柳州市科技计划项目(2024AA0203A001);广西汽车零部件与整车技术重点实验室自主课题(2023GKLACVTKF03)

Al-doped P2-type Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂ as Cathode for Sodium-ion Batteries: Synthesis and Electrochemical Properties

YAN Gongqin¹^,²(), WANG Chen¹, LAN Chunbo¹^,², HONG Yuxin¹, YE Weichao¹, FU Xianghui¹

1. School of Mechanical and Automotive Engineering, Guangxi University of Science and Technology, Liuzhou 545616, China
2. Guangxi Key Laboratory of Automobile Components and Vehicle Technology, Liuzhou 545616, China

Received:2024-12-02 Revised:2025-02-03 Published:2025-09-20 Online:2025-03-06
About author:YAN Gongqin (1982-), male, associate professor. E-mail: ygq@gxust.edu.cn
Supported by:
Guangxi Natural Science Foundation(2020GXNSFAA159024);Young and Middle-aged Teacher's Research Basis Ability in Colleges of Guangxi(2022KY0350);Science & Technology Planning Projects of Liuzhou(2024AA0203A001);Opening Foundation of Guangxi Key Laboratory of Automobile Components and Vehicle Technology(2023GKLACVTKF03)

摘要/Abstract

摘要：

钠离子电池(SIBs)具有低廉的成本和良好的安全性, 在储能领域极具发展前景, 有望替代锂离子电池。P2型Ni/Mn基氧化物具有高理论容量和宽工作电压的优点, 然而, 高压下P2-O2相变和Jahn-Teller畸变严重影响了循环可逆性和结构稳定性。针对上述问题, 本研究通过高温固相法制备了不同Al掺杂量的P2型Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂, 并将其用作SIBs正极材料, 表征了它们的形貌、成分、元素价态和结构特征。研究发现, Al掺杂增强了金属-氧键(M-O键), 增大了Na层距离, 有助于Na⁺扩散和结构稳定。电化学性能测试结果表明, Al掺杂可以抑制高压相变, 触发Mn的电化学活性, 降低电荷转移电阻, 从而增强材料的电化学性能。其中, Na_0.8Ni_0.33Mn_0.62Al_0.05O₂正极表现出最佳的循环性能, 在2.0~4.2 V范围内和0.1C(1C=200 mA·g^-1)条件下循环200 次后容量保持率为87.3%, 并且具有良好的倍率性能, 在2.0~4.2 V范围内和2C条件下放电比容量达到100.9 mAh·g^-1。

关键词: 钠离子电池, Al掺杂, P2型正极, 镍锰基氧化物, 电化学性能

Abstract:

Sodium-ion batteries (SIBs) have emerged as a significant alternative to lithium-ion batteries, offering a cost-effective and safe solution with promising potential in energy storage. Among these, P2-type Ni/Mn based oxides possess the advantages of high theoretical capacity and wide operating voltage. However, the P2-O2 phase transition under high voltage and Jahn-Teller aberration significantly impact the cycling reversibility and structural stability. To address the above issues, here, P2-type Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂ materials with different doping contents of Al using a high-temperature solid-phase method were prepared, and employed as cathodes for sodium-ion batteries. It was observed that Al doping resulted in strengthening of their metal-oxygen bonds (M-O bonds) and expansion of the distance of Na layer, thereby facilitating Na⁺ diffusion and enhancing structural stability. The electrochemical properties demonstrated that Al doping could impede the high-voltage phase transition, stimulate the electrochemical activity of Mn, and diminish the charge transfer resistance, leading to enhanced electrochemical properties of the materials. Among these P2-type Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂ materials, Na_0.8Ni_0.33Mn_0.62Al_0.05O₂ cathode displayed the optimal cycling performance with a capacity retention of 87.3% after 200 cycles at 0.1C (1C=200 mA·g^-1) in the range of 2.0-4.2 V, and the superior rate performance with a discharge specific capacity of 100.9 mAh·g^-1 at 2C in the range of 2.0-4.2 V.

Key words: sodium-ion battery, Al doping, P2-type cathode, nickel-manganese oxide, electrochemical property

中图分类号:

TB34

闫共芹, 王晨, 蓝春波, 洪雨昕, 叶维超, 付向辉. Al掺杂P2型Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂钠离子电池正极材料的制备与电化学性能[J]. 无机材料学报, 2025, 40(9): 1005-1012.

YAN Gongqin, WANG Chen, LAN Chunbo, HONG Yuxin, YE Weichao, FU Xianghui. Al-doped P2-type Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂ as Cathode for Sodium-ion Batteries: Synthesis and Electrochemical Properties[J]. Journal of Inorganic Materials, 2025, 40(9): 1005-1012.

图/表 10

图1 NMAx样品的结构模型

Fig. 1 Structural model of NMAx (a) Polyhedral structural model; (b) Ball-and-stick structural model

图2 NMAx (x=0, 0.025, 0.05, 0.1)样品的XRD图谱

Fig. 2 XRD patterns of NMAx (x=0, 0.025, 0.05, 0.1) (a) Survey XRD patterns; (b) Regional enlargement patterns in the range of 2θ=15°-17°

图3 NMAx(x=0, 0.025, 0.05, 0.1)样品的SEM照片及EDS谱图

Fig. 3 SEM images and EDS spectra of NMAx (x=0, 0.025, 0.05, 0.1) (a-d) SEM images of (a) NMA0, (b) NMA0.025, (c) NMA0.05, and (d) NMA0.1; (e, f) EDS spectra of (e) NMA0 and (f) NMA0.05; (g1-g5) EDS elemental mappings of NMA0.05

图4 NMA0、NMA0.05样品的XPS图谱

Fig. 4 XPS spectra for NMA0 and NMA0.05 (a) Survey XPS spectra; (b-d) Refined XPS spectra of (b) Mn2p, (c) Ni2p, and (d) Al2p

图5 NMAx(x=0, 0.025, 0.05, 0.1)样品的电化学性能

Fig. 5 Electrochemical performance of NMAx (x=0, 0.025, 0.05, 0.1) (a-d) GCD curves of SIBs with NMAx as cathodes for the 1st, 5th, and 100th cycles at 0.1C; (e) Cycling performance at 0.1C; (f) Rate performance. Colorful figures are available on website

图6 以NMAx(x=0, 0.025, 0.05, 0.1)为正极的SIBs在2.0~4.2 V电压范围内和0.1 mV·s-1扫描速率下的CV曲线

Fig. 6 CV curves of SIBs with NMAx (x=0, 0.025, 0.05, 0.1) as cathodes at 0.1 mV·s-1 within a voltage range of 2.0-4.2 V Colorful figures are available on website

图7 以NMAx(x=0, 0.025, 0.05, 0.1)为正极的SIBs的Nyquist谱图

Fig. 7 Nyquist plots of SIBs with NMAx (x=0, 0.025, 0.05, 0.1) as cathodes

表S1 NMAx样品的MO2层、Na层距离及晶格参数

Table S1 Distances of MO2 layers, Na layers and lattice parameters of NMAx samples

Sample	a/Å	b/Å	c/Å	α/(°)	β/(°)	γ/(°)	MO₂ layer /Å	Na layer/Å
NMA₀	3.524154	3.524154	10.279081	90	90	120	2.143	2.997
NMA_0.025	3.514988	3.514988	10.281807	90	90	120	2.139	3.002
NMA_0.05	3.511682	3.511682	10.281813	90	90	120	2.128	3.013
NMA_0.1	3.501512	3.501512	10.282081	90	90	120	2.118	3.023

表S2 NMAx(x=0, 0.025, 0.05, 0.1)第1、5、100次循环的放电比容量和库仑效率

Table S2 Discharge specific capacity and Coulombic efficiency of NMAx (x=0, 0.025, 0.05, 0.1) for the 1st, 5th, and 100th cycles

Sample	Cycle number	Discharge specific capacity/(mAh·g^-1)	Coulombic efficiency/%
NMA₀	1st	80.7	98.07
	5th	80.1	98.74
	100th	65.2	99.45
NMA_0.025	1st	87.7	98.53
	5th	87.5	98.74
	100th	82.6	99.68
NMA_0.05	1st	111.6	98.11
	5th	111.5	98.42
	100th	105.5	99.01
NMA_0.1	1st	98.5	98.85
	5th	98.1	99.25
	100th	93.3	99.54

表S3 NMAx(x=0, 0.025, 0.05, 0.1)样品的欧姆电阻(Rs)和电荷转移电阻(Rct)

Table S3 Ohmic resistance (Rs) and charge transfer resistance (Rct) of NMAx (x=0, 0.025, 0.05, 0.1) samples

Sample	R_s/Ω	R_ct/Ω
NMA₀	26.57	497.4
NMA_0.025	5.912	459.6
NMA_0.05	7.725	414.2
NMA_0.1	15.23	422.9

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Al掺杂P2型Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂钠离子电池正极材料的制备与电化学性能

Al-doped P2-type Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂ as Cathode for Sodium-ion Batteries: Synthesis and Electrochemical Properties

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