Al-doped P2-type Na0.8Ni0.33Mn0.67-xAlxO2 as Cathode for Sodium-ion Batteries: Synthesis and Electrochemical Properties

doi:10.15541/jim20240499

Abstract

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

CLC Number:

TB34

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.

Figures/Tables 10

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

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°

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

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

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

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

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

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

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

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

References 33

[1]	ŞEN M, ÖZCAN M, EKER Y R. A review on the lithium-ion battery problems used in electric vehicles. Next Sustainability, 2024, 3: 100036.
[2]	KHAN F M N U, RASUL M G, SAYEM A S M, et al. Design and optimization of lithium-ion battery as an efficient energy storage device for electric vehicles: a comprehensive review. Journal of Energy Storage, 2023, 71: 108033.
[3]	LIU J H, WANG P, GAO Z, et al. Review on electrospinning anode and separators for lithium ion batteries. Renewable and Sustainable Energy Reviews, 2024, 189: 113939.
[4]	GAO H, ZENG J, SUN Z, et al. Advances in layered transition metal oxide cathodes for sodium-ion batteries. Materials Today Energy, 2024, 42: 101551.
[5]	YU T, LI G, DUAN Y, et al. The research and industrialization progress and prospects of sodium ion battery. Journal of Alloys and Compounds, 2023, 958: 170486.
[6]	CHEN X, LIN G, LIU P, et al. Synergetic enhancement of structural stability and kinetics of P’2-type layered cathode for sodium-ion batteries via cation-anion co-doping. Energy Storage Materials, 2024, 67: 103303.
[7]	MATHIYALAGAN K, SHIN D, LEE Y C. Difficulties, strategies, and recent research and development of layered sodium transition metal oxide cathode materials for high-energy sodium-ion batteries. Journal of Energy Chemistry, 2024, 90: 40.
[8]	LU Y, SONG M, HUANG J, et al. K/Zn dual-site doping toward ultralow-strain P2-type Ni/Mn-based cathode materials for sodium- ion batteries. Journal of Energy Storage, 2024, 77: 109933.
[9]	WANG H, YANG B, LIAO X Z, et al. Electrochemical properties of P2-Na_2/3[Ni_1/3Mn_2/3]O₂ cathode material for sodium ion batteries when cycled in different voltage ranges. Electrochimica Acta, 2013, 113: 200.
[10]	LUO R, ZHANG N, WANG J, et al. Insight into effects of divalent cation substitution stabilizing P2-Type layered cathode materials for sodium-ion batteries. Electrochimica Acta, 2021, 368: 137614.
[11]	ANILKUMAR A, NAIR N, NAIR S V, et al. Tailoring high Na content in P2-type layered oxide cathodes via Cu-Li dual doping for sodium-ion batteries. Journal of Energy Storage, 2023, 72: 108291.
[12]	YANG L, LUO S H, WANG Y, et al. Cu-doped layered P2-type Na_0.67Ni_0.33-_xCu_xMn_0.67O₂ cathode electrode material with enhanced electrochemical performance for sodium-ion batteries. Chemical Engineering Journal, 2021, 404: 126578.
[13]	LI Z Y, ZHANG J, GAO R, et al. Unveiling the role of Co in improving the high-rate capability and cycling performance of layered Na_0.7Mn_0.7Ni_0.3-_xCo_xO₂ cathode materials for sodium-ion batteries. ACS Applied Materials & Interfaces, 2016, 8(24): 15439.
[14]	SUN J, SHEN J, WANG T. Electrochemical study of Na_0.66Ni_0.33-Mn_0.67-_xMo_xO₂ as cathode material for sodium-ion battery. Journal of Alloys and Compounds, 2017, 709: 481.
[15]	SU G, ZHENG H, CHEN H, et al. Ca/Mg dual-doping P2-type Na_0.67Ni_0.17Co_0.17Mn_0.66O₂ cathode material for sodium ion batteries. Materials Letters, 2023, 331: 133425.
[16]	YU L, CHENG Z, XU K, et al. Interlocking biphasic chemistry for high-voltage P2/O3 sodium layered oxide cathode. Energy Storage Materials, 2022, 50: 730.
[17]	XU J, LEE D H, CLÉMENT R J, et al. Identifying the critical role of Li substitution in P2-Na_x[Li_yNi_zMn_1-_y_-_z]O₂ (0 < x, y, z < 1) intercalation cathode materials for high-energy Na-ion batteries. Chemistry of Materials, 2014, 26(2): 1260.
[18]	FU J, HUANG H, SHI K, et al. Al-doped walnut-shell-like P2-type Na_2/3Ni_1/3Co_(1/3-_x₎Mn_1/3Al_xO₂ as advanced sodium ion battery cathode materials with enhanced rate and cycling performance. Electrochimica Acta, 2020, 349: 136347.
[19]	LIU J, QIN W, YANG Z, et al. Enhanced structural and cycling stability of O3-type NaNi_1/3Mn_1/3Fe_1/3O₂ cathode by Al replacement of Mn studied in half cell/full sodium-ion batteries. Journal of Alloys and Compounds, 2023, 933: 167714.
[20]	PENG B, CHEN Y, ZHAO L, et al. Regulating the local chemical environment in layered O3-NaNi_0.5Mn_0.5O₂ achieves practicable cathode for sodium-ion batteries. Energy Storage Materials, 2023, 56: 631.
[21]	LI G, ZHU W, LIU W. First-principles calculations of the Ti-doping effects on layered NaNiO₂ cathode materials for advanced Na-ion batteries. Journal of the Indian Chemical Society, 2022, 99(5): 100424.
[22]	ZHAO C, WANG Q, YAO Z, et al. Rational design of layered oxide materials for sodium-ion batteries. Science, 2020, 370(6517): 708. DOI PMID
[23]	ZHOU C, YANG L, ZHOU C, et al. Fluorine-substituted O3-type NaNi_0.4Mn_0.25Ti_0.3Co_0.05O_2-_xF_x cathode with improved rate capability and cyclic stability for sodium-ion storage at high voltage. Journal of Energy Chemistry, 2021, 60: 341.
[24]	ZHOU J, LIU J, LI Y, et al. Reaching the initial coulombic efficiency and structural stability limit of P2/O3 biphasic layered cathode for sodium-ion batteries. Journal of Colloid and Interface Science, 2023, 638: 758.
[25]	XU J, CHEN J, ZHANG K, et al. Na_x(Cu-Fe-Mn)O₂ system as cathode materials for Na-ion batteries. Nano Energy, 2020, 78: 105142.
[26]	QIAO D, ZHANG Y, SU C, et al. Study on the different effects of aluminum doping on Fe-Mn and Ni-Mn based compounds as cathode material for sodium-ion batteries. Journal of Industrial and Engineering Chemistry, 2023, 124: 287.
[27]	LIU J, ZHOU J, ZHAO Z, et al. Deciphering the formation process and electrochemical behavior of novel P2/O3 biphasic layered cathode with long cycle life for sodium-ion batteries. Journal of Power Sources, 2023, 560: 232686.
[28]	JIANG C, CHEN B, XU M, et al. Elevating both capacity and voltage tolerance of P2-type layered cathodes with cooperative Al cation/F anion co-doping for advanced sodium-ion batteries. Energy Storage Materials, 2024, 70: 103518.
[29]	YANG Y, YAN C, HUANG J. Research progress of solid electrolyte interphase in lithium batteries. Acta Physico Chimica Sinica, 2021, 37(11): 2010076.
[30]	FENG L, LIU Y, ZHANG D, et al. Al substituted Mn position on Li[Ni_0.5Co_0.2Mn_0.3]O₂ for high rates performance of cathode material. Vacuum, 2021, 188: 110168.
[31]	LI G, ZHANG Z, WANG R, et al. Effect of trace Al surface doping on the structure, surface chemistry and low temperature performance of LiNi_0.5Co_0.2Mn_0.3O₂ cathode. Electrochimica Acta, 2016, 212: 399.
[32]	WEN Y, WANG B, ZENG G, et al. Electrochemical and structural study of layered P2-type Na_2/3Ni_1/3Mn_2/3O₂ as cathode material for sodium-ion battery. Chemistry-An Asian Journal, 2015, 10(3): 661.
[33]	SHI S, YANG B, BAI S, et al. Ti-doped O3-NaNi_0.5Mn_0.5O₂ as high-performance cathode materials for sodium-ion batteries. Solid State Ionics, 2024, 411: 116554.

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

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 33

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	WAN Junchi, DU Lulu, ZHANG Yongshang, LI Lin, LIU Jiande, ZHANG Linsen. Structural Evolution and Electrochemical Performance of Na₄Fe_xP₄O₁₂₊_x/C Cathode Materials for Sodium-ion Batteries [J]. Journal of Inorganic Materials, 2025, 40(5): 497-503.
[2]	ZHANG Jiguo, WU Tian, ZHAO Xu, YANG Fan, XIA Tian, SUN Shien. Improvement of Cycling Stability of Cathode Materials and Industrialization Process for Sodium-ion Batteries [J]. Journal of Inorganic Materials, 2025, 40(4): 348-362.
[3]	YANG Shuqi, YANG Cunguo, NIU Huizhu, SHI Weiyi, SHU Kewei. GeP₃/Ketjen Black Composite: Preparation via Ball Milling and Performance as Anode Material for Sodium-ion Batteries [J]. Journal of Inorganic Materials, 2025, 40(3): 329-336.
[4]	ZHU Zhijie, SHEN Mingyuan, WU Tao, LI Wencui. Inhibition of P2-O2 Phase Transition for P2-Na_2/3Ni_1/3Mn_2/3O₂ as Cathode of Sodium-ion Battery via Synergetic Substitution of Cu and Mg [J]. Journal of Inorganic Materials, 2025, 40(2): 184-195.
[5]	SHEN Hao, CHEN Qianqian, ZHOU Boxiang, TANG Xiaodong, ZHANG Yuanyuan. Preparation and Energy Storage Properties of A-site La/Sr Co-doped PbZrO₃ Thin Films [J]. Journal of Inorganic Materials, 2024, 39(9): 1022-1028.
[6]	LI Jiaqi, LI Xiaosong, LI Xuanhe, ZHU Xiaobing, ZHU Aimin. Transition Metal-doped Manganese Oxide: Synthesis by Warm Plasma and Electrocatalytic Performance for Oxygen Evolution Reaction [J]. Journal of Inorganic Materials, 2024, 39(7): 835-844.
[7]	ZHOU Jingyu, LI Xingyu, ZHAO Xiaolin, WANG Youwei, SONG Erhong, LIU Jianjun. Rate and Cycling Performance of Ti and Cu Doped β-NaMnO₂ as Cathode of Sodium-ion Battery [J]. Journal of Inorganic Materials, 2024, 39(12): 1404-1412.
[8]	LI Gaoran, LI Hongyang, ZENG Haibo. Recent Progress of Boron-based Materials in Lithium-sulfur Battery [J]. Journal of Inorganic Materials, 2022, 37(2): 152-162.
[9]	WANG Jing, XU Shoudong, LU Zhonghua, ZHAO Zhuangzhuang, CHEN Liang, ZHANG Ding, GUO Chunli. Hollow-structured CoSe₂/C Anode Materials: Preparation and Sodium Storage Properties for Sodium-ion Batteries [J]. Journal of Inorganic Materials, 2022, 37(12): 1344-1350.
[10]	ZHANG Xiaojun, LI Jiale, QIU Wujie, YANG Miaosen, LIU Jianjun. Electrochemical Activity of Positive Electrode Material of P2-Na_x[Mg_0.33Mn_0.67]O₂ Sodium Ion Battery [J]. Journal of Inorganic Materials, 2021, 36(6): 623-628.
[11]	ZHANG Yaping,LEI Yuxuan,DING Wenming,YU Lianqing,ZHU Shuaifei. Preparation and Photoelectrochemical Property of the Dual-ferroelectric Composited Material [J]. Journal of Inorganic Materials, 2020, 35(9): 987-992.
[12]	ZHENG Kun, LUO Yongchun, DENG Anqiang, YANG Yang, ZHANG Haiming. Microstructure and Electrochemical Property of A₂B₇-type La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1Hydrogen Storage Alloys [J]. Journal of Inorganic Materials, 2020, 35(5): 549-555.
[13]	ZHANG Ya-Ping, DING Wen-Ming, ZHU Hai-Feng, HUANG Cheng-Xing, YU Lian-Qing, WANG Yong-Qiang, LI Zhe, XU Fei. Photoelectrochemical Properties of MoSe₂ Modified TiO₂ Nanotube Arrays [J]. Journal of Inorganic Materials, 2019, 34(8): 797-802.
[14]	Yong LI, Wei-Xin HE, Xin-Yue ZHENG, Sheng-Lan YU, Hai-Tong LI, Hong-Yi LI, Rong ZHANG, Yu WANG. Prussian Blue Cathode Materials for Aqueous Sodium-ion Batteries:Preparation and Electrochemical Performance [J]. Journal of Inorganic Materials, 2019, 34(4): 365-372.
[15]	WANG Wu-Lian, ZHANG Jun, WANG Qiu-Shi, CHEN Liang, LIU Zhao-Ping. High-quality Fe₄[Fe(CN)₆]₃ Nanocubes: Synthesis and Electrochemical Performance as Cathode Material for Aqueous Sodium-ion Battery [J]. Journal of Inorganic Materials, 2019, 34(12): 1301-1308.