硅酸盐学报

高负载稳定循环钠离子电池微米锡电极材料

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王钦 ¹^,² , 张艳岗 ¹ , 梁君飞 ¹ , 王华 ²

硅酸盐学报 | 第14届无机非金属材料专题研讨会专题—研究论文 2025,53(4): 785-791

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硅酸盐学报 |第14届无机非金属材料专题研讨会专题—研究论文 2025 , 53 (4) : 785 -791

高负载稳定循环钠离子电池微米锡电极材料

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王钦¹^,², 张艳岗¹, 梁君飞¹, 王华²

作者信息

^1．中北大学能源与动力工程学院，太原 030051

^2．北京航空航天大学化学学院，北京 102206

通讯作者:

梁君飞（1983—），男，教授；

王华（1983—），男，教授。

作者简介:

王钦（1998—），男，硕士研究生。

High Mass Loading and Stable Cycling Micrometer Tin Electrode Material for Sodium-Ion Batteries

Qin WANG¹^,², Yangang ZHANG¹, Junfei LIANG¹, Hua WANG²

Affiliations

^1.School of Energy and Power Engineering, North University of China, Taiyuan 030051, China

^2.School of Chemistry, BeiHang University, Beijing 102206, China

Corresponding Author:

LIANG Junfei (1983-), male, Ph.D., Professor; E-mail: junfeiliang@buaa.edu.cn;

WANG Hua (1983-), male, Ph.D., Professor. wanghua8651@buaa.edu.cn

WANG Qin (1998-), male, Master candidate. E-mail: S202216028@st.nuc.edu.cn

出版时间: 2025-04-20 doi: 10.14062/j.issn.0454-5648.20250004

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摘要

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钠离子电池微米锡（μSn）负极材料具有比容量高、易制备和成本低等优势，同时较小的比表面积有助于减少电化学副反应。但是，μSn电极在充放电过程中会因体积膨胀导致容量快速衰减，这一问题在电极材料负载量较高的情况下尤其显著，严重限制了μSn负极材料的实际应用。为了提高μSn负极在高负载量下的循环稳定性，将硬碳（HC）与μSn颗粒混合，HC如“围栏”般限制了μSn颗粒在钠化/脱钠过程中的团聚，同时其开放结构提供的空间可有效缓解Sn的体积膨胀。结果表明：在5.5 mg/cm²的高负载量下，μSn/HC复合材料经过200次循环后容量保持率高达93.3%，远超纯μSn电极40%的容量保持率。此外，μSn₃₀HC₇₀||Na₃V₂（PO₄）₃全电池在0.2 C条件下展现出104 mA·h/g的容量，能量密度达到186 W·h/kg，在0.5 C条件下循环100圈后容量保持率为88%，且在6 C的高倍率下性能依然稳定。本工作可为高负载量μSn电极材料的开发提供新策略，提升了循环稳定性和倍率性能，推进了其在钠离子电池中的商业化应用进程。

关键词

微米锡 / 钠离子电池 / 高负载量 / 循环稳定性

Abstract

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Introduction

High-capacity anode materials are essential for high-energy sodium-ion batteries. Sn anodes with their high theoretical capacity can face significant volume expansion (i.e., up to 420%) during sodiation, thus affecting material stability. Previous strategies for long-cycling micron-sized Sn are low loadings and inadequate for commercial needs. Enhancing cyclic stability under a high mass loading is thus crucial for high-performance sodium-ion batteries. In this paper, we simply mixed Sn with HC to form an HC "fence" that could prevent Sn particle reagglomeration and allow self-evolution. Adding 50% (in mass) HC boosted Sn/HC cyclic stability without shedding or cracking after 100 cycles at 70% (in mass) HC. The optimized μSn₃₀HC₇₀ delivered 1.8 mA·h/cm² at 200 mA/g and retained 93.3% capacity after 200 cycles at 500 mA/g. The μSn₃₀HC₇₀||Na₃V₂(PO₄)₃ (NVP)full cell had 186 W·h/kg energy density at 0.5 C and retained 92.11% capacity at 6 C.

Methods

A slurry was prepared via mixing Sn/HC, conductive agent (SP), and sodium alginate (SA) in deionized water in a mass ratio of 8∶1∶1. The mixture was coated onto carbon-coated aluminum foil, dried under vacuum at 80 ℃ for 12 h, and then cut into electrode disks with the diameter of 11 mm. The electrode disks with different μSn_xμHC_(100-_x₎ ratios were obtained, i.e., HC, μSn₂₀HC₈₀, μSn₃₀HC₇₀, μSn₄₀HC₆₀, and μSn₅₀HC₅₀, via adjusting Sn content in the mixed anode (x=0%, 20%, 30%, 40%, and 50%). In an argon-filled glovebox (the volume fractio of H₂O, O₂ ≤ 1×10^-6), 2325-type coin-cell half-cells were assembled with sodium as a counter/reference electrode, Celgard2500 as a separator, and 1 mol/L NaPF₆ in Bis(2-methoxy ethyl)ether as an electrolyte. The full cells of (μSn₃₀HC₇₀||NVP and μSn||NVP) were also constructed with μSn₃₀HC₇₀/μSn as an anode and NVP as a cathode. The calculations of capacity and energy density excluded the masses of binder and conductive agent.

Results and discussion

At a loading of 5.5 mg/cm², μSn experiences a rapid capacity decay, losing up to 60% after 200 cycles. However, blending 50% (in mass) HC enhances Sn/HC cyclic stability under the same conditions. The SEM images of the sample after 100 cycles show the best-preserved electrode surface morphology with 70% (in mass) of HC, absent of active material shedding or surface cracking. This indicates that 70% (in mass) of HC achieves a structural stability for Sn anode, exhibiting a promising potential for developing long-term cyclic stability. At a current density of 500 mA/g, this electrode retains 93.3% of its initial capacity after 200 cycles.

The results show that the capacity contribution of HC within the electrode material increases as the HC content increases, via comparing the voltage-capacity profiles of Sn/HC anodes with different HC proportions. The charging platforms of Sn at 0.2 V and 0.31 V merge into a platform, potentially due to the reduced transport resistance facilitated by HC. This can be further clarified via comparing the electrochemical impedance spectroscopy (EIS) data of μSn₃₀HC₇₀ and pure Sn, where the intrinsic impedance and diffusion impedance of Sn/HC both are lower than those of pure Sn.

The ex-situ X-ray Diffraction (XRD) patterns indicate the phase transitions of Sn/HC at different potentials. A peak at 2θ of 35.7° appears and disappears during the charge-discharge process, indicating the high reversibility of Sn material during cycling.

The μSn₃₀HC₇₀||NVP full cell validates Sn/HC practicality in sodium-ion batteries. achieving 186 W·h/kg energy density at 0.5 C and retains 92.11% at 6 C

Conclusions

Mixing HC with Sn effectively could enhance the cyclic stability of micron-sized Sn. This was attributed to the HC fence structure around Sn particles. The optimized μSn₃₀HC₇₀ anode had an areal capacity of 1.8 m·h/cm² at a current density of 200 mA/g and retained 93.3% after 200 cycles at a current density of 500 mA/g. The full cell assembled with NVP maintained a capacity retention of 92.11% after 100 cycles at 0.5 C, further validating the effectiveness of the HC "fence" structure design in improving the stability of Sn anodes under high-mass loading conditions.

Key words

micrometer-sized tin / sodium-ion battery / high-loading / cycle stability

引用本文

王钦, 张艳岗, 梁君飞, 王华. 高负载稳定循环钠离子电池微米锡电极材料. 硅酸盐学报, 2025 , 53 (4) : 785 -791 . DOI: 10.14062/j.issn.0454-5648.20250004

Qin WANG, Yangang ZHANG, Junfei LIANG, Hua WANG. High Mass Loading and Stable Cycling Micrometer Tin Electrode Material for Sodium-Ion Batteries[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (4) : 785 -791 . DOI: 10.14062/j.issn.0454-5648.20250004

基金

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山西省科技成果转化引导专项(202304021301032)
山西省基础研究计划(202403021211075)

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2025年第53卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250004

接收时间：2025-01-02
首发时间：2026-10-22
出版时间：2025-04-20

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出版历史

收稿日期：2025-01-02
修回日期：2025-01-14

基金

山西省科技成果转化引导专项(202304021301032)

山西省基础研究计划(202403021211075)

作者信息

^1．中北大学能源与动力工程学院，太原 030051

^2．北京航空航天大学化学学院，北京 102206

通讯作者:

梁君飞（1983—），男，教授；

王华（1983—），男，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250004

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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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