不同预钠化比例对AC//HC型钠离子电容器的性能影响

doi:10.19799/j.cnki.2095-4239.2024.0989

摘要/Abstract

摘要：

本工作以镍铁锰酸钠(NaNi_0.4Mn_0.4Fe_0.2O₂，NMF)作为钠源，将不同比例的钠离子预掺杂到活性炭//硬碳(AC//HC)型钠离子电容器的HC负极，通过各项测试，研究分析了不同预钠化比例对钠离子电容器的电化学性能影响。结果表明，预钠化比例提高至50%以上，AC//HC型钠离子电容器各项性能均得到显著提升，包含电压、直流内阻、容量、倍率性能、功率密度和循环性能等。当预钠化比例提高至80%时，在电压区间内呈现较好的线性曲线，放电容量达到83.73 mAh，与预钠化比例为0的电容器相比提升了3倍。以0.1 A(1.5C)的放电能量为基准计算不同电流下的放电能量保持率，大倍率电流3 A(44C)下的放电能量保持率达到79.35%，而预钠化比例为0的电容器在3 A(44C)电流下的放电能量保持率仅为26.35%。此外，当预钠化比例从0提高至80%时，功率密度从9807.89 W/kg提高至24498.51 W/kg。预钠化比例高于50%的电容器循环3000圈时的能量保持率仍然高于90%，且胀气程度较低。基于预钠化后的负极具有较低的OCV，能够相应地提升AC正极的工作电压范围，进而有效提高了容量和能量密度。与此同时，预钠化后的负极OCV降低，有利于形成致密的SEI膜，提高了HC负极表面SEI膜的稳定性。需要指出的是，预钠化比例需要控制在合适的范围内，以确保实现电容器电化学性能的最优化。本工作的研究结果为预钠化钠离子电容器的产业化进程提供了一定的科学基础。

关键词: 钠离子电容器, 预钠化, 镍铁锰酸钠, 活性炭, 硬碳

Abstract:

In this work, NaNi_0.4Mn_0.4Fe_0.2O₂ (NMF) was used as the sodium-ion source for insertion into a hard carbon (HC) anode material. Various amounts of sodium ions were pre-doped into the HC electrode to achieve different pre-sodiation ratios. AC//HC sodium-ion capacitors were fabricated using an activated carbon (AC) cathode and a pre-sodiated HC anode. The influence of different pre-sodiation ratios on electrochemical performance was analyzed through electrochemical tests. Results indicated that sodium-ion capacitors with a pre-sodiation ratio above 50% exhibited significantly improved performance, including higher voltage, lower direct current internal resistance, enhanced capacity, superior rate performance, and increased power and cycle stability. With a pre-sodiation ratio of 80%, the capacitor demonstrated a linear charge-discharge profile over the voltage range. Additionally, the discharge capacity increased to 83.73 mAh, which was three times that of a capacitor with 0 pre-sodiation. In terms of rate performance, the discharge energy retention at 3 A (44C) improved significantly to 79.35% compared to that at 0.1 A (1.5C), whereas the capacitor with 0 pre-sodiation retained only 26.35% under the same conditions. Furthermore, as the pre-sodiation ratio increased from 0 to 80%, the power density rose from 9807.89 W/kg to 24498.51 W/kg. Capacitors with a 50% pre-sodiation ratio retained more than 90% of their initial energy after 3000 cycles, and their gas expansion degree was lower than that of capacitors with a pre-sodiation ratio below 30%. The lower open-circuit voltage (OCV) of the HC anode due to pre-sodiation increased the operating voltage range of the AC cathode, effectively enhancing the capacity and energy density of the AC//HC sodium-ion capacitor. Additionally, the lower OCV facilitated the formation of a dense solid electrolyte interphase (SEI) layer, improving its stability and cycle performance. However, controlling the pre-sodiation ratio within an optimal range is crucial to achieving the best electrochemical performance. This research provides a scientific basis for the industrial implementation of sodium-ion capacitor pre-sodiation.

Key words: sodium-ion capacitors, pre-sodiation, sodium nickel iron manganese oxide, activated carbon, hard carbon

中图分类号:

TM 911

安仲勋, 梁鹏程, 杨重阳. 不同预钠化比例对AC//HC型钠离子电容器的性能影响[J]. 储能科学与技术, 2025, 14(4): 1679-1686.

Zhongxun AN, Pengcheng LIANG, Chongyang YANG. The influence of different pre-sodiation ratios on the performance of AC//HC sodium-ion capacitors[J]. Energy Storage Science and Technology, 2025, 14(4): 1679-1686.

图/表 6

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参考文献 15

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