硅酸盐学报

一步法实现Al₂O₃包覆：协同优化循环性能与倍率性能

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李帅 ¹ , 黄胜壹 ¹ , 杨国凤 ¹ , 何永斌 ³ , 陈绍军 ² , 肖顺华 ¹

硅酸盐学报 | 研究论文 2026,54(7): 2458-2469

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硅酸盐学报 |研究论文 2026 , 54 (7) : 2458 -2469

一步法实现Al₂O₃包覆：协同优化循环性能与倍率性能

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李帅¹, 黄胜壹¹, 杨国凤¹, 何永斌³, 陈绍军², 肖顺华¹

作者信息

^1．桂林理工大学化学与生物工程学院，广西高校表面与界面电化学重点实验室，广西电化学与磁化学功能材料重点实验室，广西桂林 541004

^2．河源职业技术学院机电工程学院，广东河源 517000

^3．柳州国轩电池有限公司，广西柳州 545616

通讯作者:

肖顺华（1969—），男，博士，教授；

陈绍军（1982—），男，硕士，教授。

作者简介:

李帅（2002—），男，硕士研究生。

Preparation of Al₂O₃ Coating for Sodium-ion Batteries via One-step Approach

Shuai LI¹, Shengyi HUANG¹, Guofeng YANG¹, Yongbin HE³, Shaojun CHEN², Shunhua XIAO¹

Affiliations

^1.Guangxi Colleges and Universities Key Laboratory of Surface and Interface Electrochemistry, Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, Guangxi, China

^2.College of Mechanical and Electrical Engineering, Heyuan Polytechnic, Heyuan 517000, Guangdong, China

^3.Liuzhou Gotion Battery Co.Ltd, Liuzhou 545616, Guangxi, China

Corresponding Author:

XIAO Shunhua (1969-), male, Ph.D., Professor. E-mail: 1999014@glut.edu.cn;

CHEN Shaojun (1982-), male, Master, Professor. 277489319@qq.com

LI Shuai (2002-), male, Master candidate. E-mail: 2893327768@qq.com

出版时间: 2026-06-02 doi: 10.14062/j.issn.0454-5648.20250844

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摘要

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NaNi_1/3Fe_1/3Mn_1/3O₂（NFM）作为钠离子电池正极材料，虽具备环境友好、毒性低及原料丰度高等商业化潜力优势，但其结构稳定性不足导致循环性能衰减、倍率性能较差，制约了实际应用。针对这些问题，本工作采用湿化学法结合高温固相法在NFM正极材料表面包覆Al₂O₃层，通过包覆层抑制电极-电解质界面副反应并维持Na⁺扩散通道完整性，同时提升材料循环稳定性与倍率性能。电化学测试显示，以Al₂O₃包覆的NFM为正极材料的钠离子电池在2 C（1 C=150 mA/g）倍率下循环150次容量保持率达82.77%，在5 C倍率下循环300次容量保持率达73.31%，显著改善了循环稳定性。在0.1~10.0 C倍率范围内，NFM包覆Al₂O₃层钠离子电池在10 C高倍率下放电容量达98.0 mA·h·g^-1 （NFM钠离子电池仅为56.26 mA·h·g^-1），且当倍率回调至0.1 C时，容量恢复至初始值的92.1%（137.16 mA·h·g^-1），材料的结构可逆性提升，进而增强了器件的倍率性能。这些结果证实，Al₂O₃包覆策略通过调控界面反应与离子传输，充分激发了NFM正极材料的电化学潜能，进而提升了钠离子电池的稳定性。

关键词

层状氧化物正极材料 / 钠离子电池 / 氧化铝包覆 / 电化学机制 / 循环性能 / 倍率性能

Abstract

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Introduction

Sodium-ion batteries (SIBs) have attracted much attention as a promising alternative to lithium-ion batteries due to the abundance and low cost of sodium resources. Among various cathode materials, layered oxide NaNi_1/3Fe_1/3Mn_1/3O₂ (NFM) offers some advantages such as environmental friendliness, low toxicity, and high theoretical capacity. However, its practical application is severely hindered by structural instability, poor cycling stability, and inferior rate capability, which originate mainly from undesirable

electrode-electrolyte interfacial side reactions, irreversible phase transitions during Na⁺ insertion/extraction, and sluggish Na⁺diffusion kinetics. Surface coating is considered as an effective strategy to address these issues. In particular, Al₂O₃ coatings can suppress parasitic reactions and stabilize the layered structure. Nevertheless, conventional coating methods often involve complex, multi-step processes such as atomic layer deposition (ALD) or post-annealing, which are costly and less scalable. In this work, we developed a facile one-step wet-chemical route combined with solid-state calcination to obtain an Al₂O₃ coating on NFM. The aim was to simultaneously enhance the cycling stability and rate capability via forming a protective layer, while enabling partial Al³⁺doping into the near-surface lattice. In addition, the underlying mechanism was also investigated.

Methods

The pristine NFM material was synthesized via mixing Ni_1/3Fe_1/3Mn_1/3(OH)₂ precursor with Na₂CO₃ (molar ratio 1.000∶0.525), followed by pre-sintering at 500 ℃ for 5 h, and then calcined in O₂ atmosphere at 850 ℃ for 15 h. For Al₂O₃ coating, different molar fractions (0.5%, 1.0%, and 2.0%) of Al(NO₃)₃·9H₂O were dissolved in ethanol, and the precursor was added. The mixture was stirred, ultrasonicated, and then dried at 70 ℃ and then at 120 ℃. The obtained Al-precoated precursor was calcined under the same conditions as the pristine NFM, obtaining the samples denoted as NFM-0.5A, NFM-1A, and NFM-2A, respectively.

CR2032 coin-type half-cells were assembled in an argon-filled glove box (Mikrouna Super 1220/750/900, China) using sodium metal as a counter electrode, glass fiber as a separator, and 1.0 mol/L NaClO₄ in ethylene carbonate (EC)/propylene carbonate (PC) (1∶1 by volume) with 5% (in mass fraction) fluoroethylene carbonate (FEC) as an electrolyte. The working electrode consisted of 80% (in mass fraction) active material, 10% (in mass fraction) carbon black, and 10% (in mass fraction) polyvinylidene fluoride (PVDF) in N-methyl-2-pyrrolidone (NMP, ca. 1.0-1.5 mL).

The crystal structure was characterized by X-ray diffraction (XRD) with Rietveld refinement. The surface morphology and element distribution were determined by scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The surface chemical states were analyzed by X-ray photoelectron spectroscopy (XPS). The electrochemical performance (i.e., the cycling stability at various rates (i.e., 1, 2, and 5 C) and the rate capability from 0.1 C to 10.0 C) were evaluated by a battery test system. The electrochemical impedance spectroscopy (EIS) was performed at 0.01-100.00 kHz with an amplitude of 5 mV. The Na⁺ diffusion coefficient was determined by galvanostatic intermittent titration technique (GITT).

Results and discussion

The XRD patterns of pristine NFM and NFM-1A show no impurity peaks, both exhibiting an O3-type α-NaFeO₂ layered structure with a space group . The peaks (003) and (104) of NFM-1A shift slightly, and the Rietveld refinement reveals increased lattice parameters a, c, and cell volume (from 2.980 Å, 15.960 Å, and 122.755 Å³ for NFM to 2.983 Å, 15.988 Å, and 123.160 Å³ for NFM-1A), indicating partial Al³⁺ doping into the near-surface lattice, which expands the interlayer spacing and facilitates Na⁺ transport.

The SEM images show that NFM-1A and NFM-2A have a uniform coating layer. The TEM images and EDS spectra indicate a distinct Al₂O₃ coating layer with a thickness of approximately 15 nm on the NFM surface, and a small amount of Al³⁺ diffuses into the shallow lattice, forming strong Al-O bonds. The XPS analysis further shows the presence of Al₂O₃ on the surface, as evidenced by the Al 2p peak at 73.08 eV. The binding energies of Ni 2p, Fe 2p, and Mn 2p in NFM-1A shift slightly to lower values, compared with pristine NFM, which is attributed to a charge compensation from Al³⁺ incorporation, thus stabilizing the structure.

The results of electrochemical tests demonstrate that the NFM-1A electrode exhibits the optimum overall performance. The initial discharge capacities at 0.1 C are 140.53, 143.34, 145.99 mA·h·g^-1, and 140.48 mA·h·g^-1 for NFM, NFM-0.5A, NFM-1A, and NFM-2A, respectively, with the corresponding Coulombic efficiencies of 88.67%, 86.06%, 90.78%, and 87.62%. After 150 cycles at 1 C, the discharge capacities are 91.83, 104.46, 113.38 mA·h·g^-1, and 99.80 mA·h·g^-1, with the capacity retentions of 68.62%, 77.14%, 80.77%, and 77.16%, respectively. At a higher rate of 2 C, NFM-1A retains 82.77% of its initial capacity after 150 cycles (112.42 mA·h·g^-1), and at 5 C, it retains 73.31% after 300 cycles (92.20 mA·h·g^-1). The results of rate capability test show that NFM-1A delivers a discharge capacity of 98.0 mA·h·g^-1 at 10 C, far exceeding that of pristine NFM (56.26 mA·h·g^-1). When the rate is 0.1 C, NFM-1A recovers 92.1% of its initial capacity (137.16 mA·h·g^-1), demonstrating the excellent structural reversibility.

The GITT measurements reveal that the average Na⁺ diffusion coefficient of NFM-1A (1.20×10^-10 cm²/s) is approximately twice greater than that of pristine NFM (5.89×10^-11 cm²/s), confirming that the Al₂O₃ coating with partial Al³⁺ doping broadens the Na⁺transport channels. The EIS analysis shows that after 150 cycles, the charge transfer resistance (R_ct) of NFM-1A (347.40 Ω) is significantly lower than that of pristine NFM (544.48 Ω), and the conductive interface resistance (R_f) is also reduced (262.80 Ω vs. 344.39 Ω). The post-cycling XRD patterns and SEM images indicate that NFM-1A maintains better crystallinity and intact spherical particle morphology without cracks, whereas pristine NFM exhibits severe particle fragmentation. These results confirm that the Al₂O₃ coating effectively suppresses interfacial side reactions, stabilizes the layered structure, and preserves the integrity of secondary particles during prolonged cycling.

Conclusions

An Al₂O₃-coated NFM cathode material was prepared by a one-step wet-chemical method and subsequent solid-state calcination. The optimal coating amount was 1% (in mole fraction) (NFM-1A). The Al₂O₃ coating acted as a physical barrier to suppress electrode-electrolyte interfacial side reactions and, simultaneously, partial Al³⁺ doping into the near-surface lattice formed strong Al-O bonds, expanded the interlayer spacing, and enhanced Na⁺ diffusion kinetics. Consequently, NFM-1A exhibited significantly improved cycling stability (i.e., retention after 150 cycles of 80.77% at 1 C, 82.77% at 2 C, and 73.31% at 5 C) and outstanding rate capability (i.e., 98.0 mA·h·g^-1 at 10 C with capacity recovery of 92.1%). This work could provide a simple and scalable strategy for developing high-performance layered oxide cathodes for sodium-ion batteries.

Key words

layered oxide cathode material / sodium-ion battery / alumina coating / electrochemical mechanism / cycling performance / rate capability

引用本文

李帅, 黄胜壹, 杨国凤, 何永斌, 陈绍军, 肖顺华. 一步法实现Al₂O₃包覆：协同优化循环性能与倍率性能. 硅酸盐学报, 2026 , 54 (7) : 2458 -2469 . DOI: 10.14062/j.issn.0454-5648.20250844

Shuai LI, Shengyi HUANG, Guofeng YANG, Yongbin HE, Shaojun CHEN, Shunhua XIAO. Preparation of Al₂O₃ Coating for Sodium-ion Batteries via One-step Approach[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (7) : 2458 -2469 . DOI: 10.14062/j.issn.0454-5648.20250844

基金

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国家自然科学基金(22362011; 22169007)
广东省普通高校创新团队项目(2025KCXTD091)

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2026年第54卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250844

接收时间：2025-11-17
首发时间：2026-10-22
出版时间：2026-06-02

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收稿日期：2025-11-17
修回日期：2025-12-25

基金

国家自然科学基金(22362011; 22169007)

广东省普通高校创新团队项目(2025KCXTD091)

作者信息

^1．桂林理工大学化学与生物工程学院，广西高校表面与界面电化学重点实验室，广西电化学与磁化学功能材料重点实验室，广西桂林 541004

^2．河源职业技术学院机电工程学院，广东河源 517000

^3．柳州国轩电池有限公司，广西柳州 545616

通讯作者:

肖顺华（1969—），男，博士，教授；

陈绍军（1982—），男，硕士，教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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