中空海胆状Ni-Co MOF/PP改性隔膜的制备及电化学性能研究

doi:10.19799/j.cnki.2095-4239.2025.0550

储能科学与技术 ›› 2025, Vol. 14 ›› Issue (11): 4152-4161.doi: 10.19799/j.cnki.2095-4239.2025.0550

中空海胆状Ni-Co MOF/PP改性隔膜的制备及电化学性能研究

卫丹¹(), 刘悦琳², 韩小娟¹, 陈立新³()

^1.陕西国际商贸学院医药学院，陕西咸阳 712046
^2.西安建筑科技大学材料科学与工程学院，陕西西安 710055
^3.西北工业大学化学与化工学院，陕西西安 710072

收稿日期:2025-06-10 修回日期:2025-07-24 出版日期:2025-11-28 发布日期:2025-11-24
通讯作者: 陈立新 E-mail:weidan1059@163.com;lixin@nwpu.edu.cn
作者简介:卫丹（1990—），女，博士，讲师，研究方向为锂硫电池关键材料，E-mail：weidan1059@163.com；
基金资助:
陕西省自然科学基础研究计划青年项目(2025JC-YBQN-1276);陕西省教育厅一般专项科学研究计划项目(24JK0328)

Fabrication and electrochemical performance of hollow sea-urchin-like Ni-Co MOF/PP modified separator

Dan WEI¹(), Yuelin LIU², Xiaojuan HAN¹, Lixin CHEN³()

^1.School of Pharmacy, Shaanxi University of International Trade & Commerce, Xianyang 712046, Shaanxi, China
^2.College of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, Shaanxi, China
^3.School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an 710072, Shaanxi, China

Received:2025-06-10 Revised:2025-07-24 Online:2025-11-28 Published:2025-11-24
Contact: Lixin CHEN E-mail:weidan1059@163.com;lixin@nwpu.edu.cn

摘要/Abstract

摘要：

本工作采用溶剂热法制备了中空海胆状镍钴双金属有机框架(Ni-Co MOF)材料，通过控制Ni/Co双金属配比实现了材料粒径及中空结构的可控调节，优化的Ni/Co配比能显著提升材料的比表面积并暴露更多金属活性位点，强化了与多硫化物的化学结合作用，可以有效抑制锂硫电池的穿梭效应。采用真空抽滤法制备了系列Ni-Co MOF/PP改性隔膜，并测试了其电化学性能，研究了双金属配比对电池性能的影响。当Ni/Co摩尔比为3∶7时，改性隔膜表现出最佳的倍率性能和循环稳定性，放电比容量在0.1、0.2、0.5、1和2 C下分别具有1257.6、950.6、825.6、721.4和573.8 mAh/g；在1 C长循环中，初始放电比容量为864.9 mAh/g，循环300次后放电比容量保持在537.4 mAh/g，库仑效率为95.2%，每圈容量衰减率为0.043%。该改性隔膜具有最小的极化电压差和良好的可逆性，并且在电池工作电压下的电化学稳定性、离子电导率高、Li⁺迁移数大，与多硫化物间存在显著化学结合作用，作为改性隔膜涂层可有效抑制多硫化物的迁移扩散。结果表明，该材料通过强界面吸附作用锚定活性物质显著缓解了锂硫电池的穿梭效应问题，展现出优异的电化学屏障功能。

关键词: 镍钴双金属有机框架, 改性隔膜, 穿梭效应, 锂硫电池

Abstract:

This study employed a solvothermal method to fabricate hollow, sea-urchin-like nickel-cobalt bimetallic organic framework (Ni-Co MOF) materials. By adjusting the Ni/Co bimetallic ratio, the particle size and hollow structure of the material were effectively tuned. The optimized Ni/Co ratio significantly increased the specific surface area of the material, exposing more active metal sites and strengthening the chemical interaction with polysulfides, thereby effectively suppressing the shuttle effect in lithium-sulfur (Li-S) batteries. A series of Ni-Co MOF/PP modified separators were prepared via vacuum filtration, and their electrochemical performance was evaluated to examine the influence of the bimetallic ratio on battery performance. At a Ni/Co ratio of 3∶7, the modified separator exhibited optimal rate capability and cycling stability. The discharge specific capacities reached 1257.6, 950.6, 825.6, 721.4, and 573.8 mAh/g at rates of 0.1, 0.2, 0.5, 1, and 2 C, respectively. During long-term cycling at 1 C, the initial discharge specific capacity was 864.9 mAh/g, which remained at 537.4 mAh/g after 300 cycles, with a Coulombic efficiency of 95.2% and a low per-cycle capacity decay rate of 0.043%. Furthermore, this modified separator demonstrated the smallest polarization voltage difference, excellent reversibility, high electrochemical stability within the operating voltage range, high ionic conductivity, and a large Li⁺ transference number. It also exhibited strong chemical binding interactions with polysulfides, effectively inhibiting their migration and diffusion as a modified separator coating. Overall, these results demonstrate that the material anchors active substances through strong interfacial adsorption, significantly mitigating the shuttle effect in Li-S batteries and providing superior electrochemical barrier functionality.

Key words: bimetallic nickel-cobalt metal-organic framework, modified separator, shuttle effect, lithium-sulfur batteries

中图分类号:

TM 912

卫丹, 刘悦琳, 韩小娟, 陈立新. 中空海胆状Ni-Co MOF/PP改性隔膜的制备及电化学性能研究[J]. 储能科学与技术, 2025, 14(11): 4152-4161.

Dan WEI, Yuelin LIU, Xiaojuan HAN, Lixin CHEN. Fabrication and electrochemical performance of hollow sea-urchin-like Ni-Co MOF/PP modified separator[J]. Energy Storage Science and Technology, 2025, 14(11): 4152-4161.

图/表 11

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参考文献 26

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中空海胆状Ni-Co MOF/PP改性隔膜的制备及电化学性能研究

Fabrication and electrochemical performance of hollow sea-urchin-like Ni-Co MOF/PP modified separator

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