粒径级配对干法电极阴极材料结构和性能的影响

谷婧瑜; 陈小龙; 陈海英; 陈康龙; 徐凯琪; 彭冲; 胡玉; 游腾

doi:10.19799/j.cnki.2095-4239.2026.0586

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粒径级配对干法电极阴极材料结构和性能的影响

储能材料与器件 | 更新时间：2026-07-21

- 粒径级配对干法电极阴极材料结构和性能的影响
- Effect of Particle Size Grading on the Structure and Performance of Dry Electrode Cathode Materials
- 储能科学与技术 2026年页码：1-9
- 作者机构：
  
  1.广东电网有限责任公司湛江供电局，广东湛江 524000
  2.广东新型储能国家研究院有限公司，广东广州 510080
  3.National Institute of Guangdong Advanced Energy Storage Co., Ltd., Guangzhou 510080, Guangdong, China
- 作者简介：
  
  谷婧瑜，女，本科，研究方向为电力系统自动化技术；
  游腾，硕士，研究方向为热电半导体与器件，E-mail：18669756251@163.com。
- 基金信息：
  
  南方电网公司科技项目资助(030800KC24090007)
- DOI：10.19799/j.cnki.2095-4239.2026.0586
  中图分类号： TM 911.3
- 收稿：2026-07-07，
  
  修回：2026-07-16，
  
  网络首发：2026-07-21，
- 稿件说明：
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谷婧瑜, 陈小龙, 陈海英, 等. 粒径级配对干法电极阴极材料结构和性能的影响[J]. 储能科学与技术, XXXX, XX(XX): 1-9.

Gu Jingyu, Chen Xiaolong, Chen Haiying, et al. Effect of Particle Size Grading on the Structure and Performance of Dry Electrode Cathode Materials[J]. Energy Storage Science and Technology, XXXX, XX(XX): 1-9.
谷婧瑜, 陈小龙, 陈海英, 等. 粒径级配对干法电极阴极材料结构和性能的影响[J]. 储能科学与技术, XXXX, XX(XX): 1-9. DOI： 10.19799/j.cnki.2095-4239.2026.0586.

Gu Jingyu, Chen Xiaolong, Chen Haiying, et al. Effect of Particle Size Grading on the Structure and Performance of Dry Electrode Cathode Materials[J]. Energy Storage Science and Technology, XXXX, XX(XX): 1-9. DOI： 10.19799/j.cnki.2095-4239.2026.0586.

摘要

随着高能量密度、低成本和绿色制造锂离子电池的发展需求不断提升，干法电极因省去溶剂使用和干燥过程、工艺流程短、能耗低以及适于制备厚电极等优势受到关注。然而，磷酸铁锂干法厚电极在高压实条件下容易形成高曲折度孔隙结构，导致电解液浸润不足、离子扩散路径延长和界面极化加剧，限制了其倍率性能与循环稳定性。针对干法磷酸铁锂厚电极中能量密度与传输动力学难以兼顾的问题，采用活性物质粒径级配策略调控电极微观结构。通过干粉混合、聚四氟乙烯原位剪切纤维化、多次辊压成膜及热压复合等无溶剂工艺，制备了级配粒径磷酸铁锂自支撑干法厚电极。形貌与结构表征结果表明，级配颗粒能够形成“大颗粒构建主体骨架、小颗粒填充颗粒间隙”的多模态密堆积结构，减少无效孔隙和局部闭塞孔，改善颗粒间接触并构筑连续的离子/电子传输通道。同时，小颗粒提高了局部接触面积和锚固位点密度，使聚四氟乙烯纤维在不同尺度颗粒之间形成更稳定的多点互锁网络，从而增强电极结构完整性。电化学结果显示，级配粒径电极在0.2 C下初始放电比容量达到161.6 mAh/g，高于单一粒径电极的150.8 mAh/g；在1 C、3 C、5 C和10 C下分别保持156.9、147.9、138.4和107.9 mAh/g的放电比容量，均优于对照电极。微分容量与阻抗分析表明，级配粒径电极的充放电极化电位差由0.22 V降低至0.17 V，初始电荷转移阻抗由约390 Ω降至约210 Ω，循环200圈后仍保持较低界面阻抗。在0.2 C下循环200圈后，级配粒径电极容量保持率为94.2%，明显高于单一粒径电极的81.3%。结果表明，粒径级配能够有效重塑干法厚电极孔隙网络，降低传输阻抗并提升结构稳定性，为高载量、高动力学性能磷酸铁锂干法电极的结构设计提供了依据。

Abstract

With the increasing demand for lithium-ion batteries with high energy density

low cost

and greener manufacturing

dry electrode technology has attracted considerable attention because it eliminates solvent use and drying procedures

shortens the manufacturing process

reduces energy consumption

and enables the fabrication of thick electrodes. However

dry-processed lithium iron phosphate (LFP) thick electrodes are prone to forming highly tortuous pore structures under high compaction

resulting in insufficient electrolyte infiltration

prolonged ion diffusion pathways

and intensified interfacial polarization

which restrict their rate capability and cycling stability. To address the trade-off between energy density and transport kinetics in dry-processed LFP thick electrodes

a particle-size grading strategy was adopted to regulate the electrode microstructure. Freestanding dry-processed LFP thick electrodes with graded particle sizes were fabricated through a solvent-free process involving dry powder mixing

in situ shear-induced fibrillation of polytetrafluoroethylene

repeated roll-pressing

and hot-pressing lamination. Morphological and structural characterizations reveal that the graded particles form a multimodal close-packing architecture

in which large particles construct the primary framework while small particles fill the interparticle voids. This structure reduces inactive voids and locally blocked pores

improves interparticle contact

and establishes continuous ion/electron transport pathways. Meanwhile

the introduction of small particles increases the local contact area and anchoring-site density

enabling polytetrafluoroethylene fibrils to form a more stable multipoint interlocking network among particles of different sizes

thereby enhancing the structural integrity of the electrode. Electrochemical results show that the graded-particle electrode delivers an initial discharge specific capacity of 161.6 mAh/g at 0.2 C

higher than the 150.8 mAh/g of the single-particle-size electrode. At 1 C

3 C

5 C

and 10 C

the graded-particle electrode maintains discharge capacities of 156.9

147.9

138.4

and 107.9 mAh/g

respectively

outperforming the control electrode at all tested rates. Differential capacity and impedance analyses further demonstrate that the charge-discharge polarization voltage gap decreases from 0.22 to 0.17 V

while the initial charge-transfer resistance is reduced from approximately 390 to 210 Ω. After 200 cycles

the graded-particle electrode still maintains a lower interfacial resistance. At 0.2 C

the capacity retention after 200 cycles reaches 94.2%

markedly higher than the 81.3% of the single-particle-size electrode. These results indicate that particle-size grading effectively restructures the pore network of dry-processed thick electrodes

lowers transport resistance

and improves structural stability

providing a practical microstructural design strategy for high-loading LFP dry electrodes with enhanced kinetic performance.

关键词

Keywords

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