吡啶添加剂改善磷酸铁锂储能电池循环性能研究
收稿日期: 2025-06-12
修回日期: 2025-08-11
录用日期: 2025-09-12
网络出版日期: 2025-09-12
A Novel Electrolyte Pyridine Additive for Enhancing Cycle Life of Lithium-ion Batteries
Received date: 2025-06-12
Revised date: 2025-08-11
Accepted date: 2025-09-12
Online published: 2025-09-12
锂离子电池作为储能行业的新宠，发展迅速。如何匹配光伏协同使用，做到光储同寿是行业的关注焦点之一。为匹配光伏使用寿命，储能电池的循环寿命需要与光伏持平。基于以上需求，本研究针对电池循环寿命提升进行了研究，开发了一种吡啶功能性添加剂。该添加剂优先于碳酸乙烯酯和碳酸亚乙烯酯在负极表面发生还原反应，促使负极界面形成富含氮、氟等元素的固体电解质界面膜，此界面膜能够有效抑制电解液在石墨负极表面的副反应，降低循环过程中活性锂损失，因此，吡啶的加入可以显著提升石墨||磷酸铁锂（Gr||LFP）软包电池的循环性能。同时在100%荷电状态电池高温存储的测试中，含有吡啶的电池容量衰减也有所减缓。另外，对吡啶的用量进行了评估，结果表明，使用含0.5wt% 吡啶电解液的Gr.||LFP软包电池综合性能最优。
王鹏程 , 李定昌 , 李君涛 , 卢光波 , 王铈汶 . 吡啶添加剂改善磷酸铁锂储能电池循环性能研究[J]. 电化学, 2025 , 31(12) : 2506131 . DOI: 10.61558/2993-074X.3584
Lithium-ion (Li-ion) battery using a graphite (Gr.) anode and a lithium iron phosphate (LiFePO4, LFP) cathode (Gr.||LFP) has been widespread in energy storage. To match the warranty period of energy storage systems, the lifespan of this kind of Li-ion battery, not only under room temperature but also under relatively high temperature, is critical. Exploration of functional electrolyte additive provides an efficient approach to address this issue. This study reports the usage of pyridine (Py) as a new electrolyte functional additive for Gr.||LFP. In the first cycle, it was found that Py can be reduced before ethylene carbonate and vinylene carbonate, forming a dense and homogeneous solid electrolyte interface (SEI) layer containing rich nitrogen and fluorine elements. Owing to the merits of the SEI layer, the parasitic reactions which occur at the graphite anode and consume the active lithium ion during cycling were suppressed. With the amount of 0.5wt% Py additive in the electrolyte, the Gr.||LFP pouch cell achieved a capacity of 3.2 Ah, exhibiting remarkablly enhanced cycling stability and high-temperature storage capability. Under the experimental conditions of 25 ℃and 0.5 P, the capacity retention of the pouch cell reached 95.64% after 500 cycles, while still maintained 82.75% of the initial capacity after 1000 cycles under 45 °C and 1 P. After the 30-day storage at 45 °C and 60 °C, the capacity retention rates were 87.38% and 80.56%, respectively, which are significantly higher than those of the pouch cells with the blank control electrolyte. This work identifies Py as a highly promising electrolyte additive in stabilizing the graphite-based anode of Li-ion battery under both room temperature and high temperature.
| [1] | Zhang L Q, Zhu C X, Yu S C, Ge D H, Zhou H S. Status and challenges facing representative anode materials for rechargeable lithium batteries[J]. J. Energy Chem., 2022, 66: 260-294. https://doi.org/10.1016/j.jechem.2021.08.001. |
| [2] | Goodenough J B. Energy storage materials: a perspective[J]. Energy Storage Mater., 2015, 1: 158-161. https://doi.org/10.1016/j.ensm.2015.07.001. |
| [3] | O'Heir J. Building Better Batteries[J]. Mech. Eng., 2017, 139(1): 10-11. https://www.asme.org/topics-resources/content/building-better-batteries. |
| [4] | Dunn B, Kamath H, Tarascon J M. Electrical energy storage for the grid: a battery of choices[J]. Science, 2011, 334(6058): 928-935. https://doi.org/10.1126/science.1212741. |
| [5] | Kim J H, Woo S C, Park M S, Kin K J, Yim T, Kim J S. Capacity fading mechanism of LiFePO4-based lithium secondary batteries for stationary energy storage[J]. J. Power Sources, 2013, 229: 190-197. https://doi.org/10.1016/j.jpowsour.2012.12.024. |
| [6] | Tasaki K, Goldberg A, Lian J J, Walker M, Timmons A, Harris S J. Solubility of lithium salts formed on the lithium-ion battery negative electrode surface in organic solvents[J]. J. Electrochem. Soc., 2009, 156(12): A1019-A1027. https://doi.org/10.1149/1.3239850. |
| [7] | Ding L, Bagul P, Cui L, Oswald S, Pohle B, Leones R, Mikhailova D. Graphite anode functionalized with a gel biopolymer binder for Li-ion batteries operating in a broad temperature range[J]. ACS Appl. Energy Mater., 2023, 6(8): 4404-4412. https://doi.org/10.1021/acsaem.3c00512. |
| [8] | Sharifi H, Mosallanejad B, Mohammadzad M, Hosseini-Hosseinabad S M, Ramarkrishna S. Cycling Performance of LiFePO4/graphite batteries and their degradation mechanism analysis via electrochemical and microscopic techniques[J]. Ionics, 2021, 28(1): 213-228. https://doi.org/10.1007/s11581-021-04258-9. |
| [9] | Dubarry M, Liaw B Y. Identify capacity fading mechanism in a commercial LiFePO4 cell[J]. J. Power Sources, 2009, 194(1): 541-549. https://doi.org/10.1016/j.jpowsour.2009.05.036. |
| [10] | Tan L, Zhang L, Sun Q N, Shen M, Qu Q T, Zheng H H. Capacity loss induced by lithium deposition at graphite anode for LiFePO4/graphite cell cycling at different temperatures[J]. Electrochimica Acta, 2013, 111: 802-808. https://doi.org/10.1016/j.electacta.2013.08.074. |
| [11] | Zhang Y C, Wang C Y, Tang X D. Cycling degradation of an automotive LiFePO4lithium-ion battery[J]. J. Power Sources, 2011, 196(3): 1513-1520. https://doi.org/10.1016/j.jpowsour.2010.08.070. |
| [12] | Wu H C, Su C Y, Shieh D T, Yang M H, Wu N L. Enhanced high-temperature cycle life of LiFePO4-based Li-ion batteries by vinylene carbonate as electrolyte additive[J]. Electrochem. Solid-State Lett., 2006, 9(12): A537-A541. https://doi.org/10.1149/1.2351954. |
| [13] | Song H S, Cao Z, Zhang Z A, Lai Y Q, Li J, Liu Y X. Effect of vinylene carbonate as electrolyte additive on cycling performance of LiFePO4/graphite cell at elevated temperature[J]. T. Nonferr. Metal. Soc., 2014, 24(3): 723-728. https://doi.org/10.1016/S1003-6326(14)63117-4. |
| [14] | Liu Y H, Takeda S, Kaneko I, Yoshitake H, Yanagida M, Saito Y, Sakai T. Formation of thermally resistant films induced by vinylene carbonate additive on a hard carbon anode for lithium ion batteries at elevated temperature[J]. RSC Adv., 2016, 6(79): 75777-75781. https://doi.org/10.1039/C6RA15168J. |
| [15] | Liao L X, Cheng X Q, Ma Y L, Zuo P J, Fang W, Yin G P, Gao Y Z. Fluoroethylene carbonate as electrolyte additive to improve low temperature performance of LiFePO4 electrode[J]. Electrochimica Acta, 2013, 87: 466-472. https://doi.org/10.1016/j.electacta.2012.09.083. |
| [16] | Wu B R, Ren Y H, Mu D B, Liu X J, Zhao J C, Wu F. Enhanced electrochemical performance of LiFePO4 cathode with the addition of fluoroethylene carbonate in electrolyte[J]. Electrochem. Solid-State Lett., 2012, 17(3): 811-816. https://doi.org/10.1007/s10008-012-1927-9. |
| [17] | Ma C X, Qiu Z J, Shan B H, Song Y J, Zheng R M, Feng W T, Cui Y P, Xing W. The optimization of the electrolyte for low temperature LiFePO4-graphite battery[J]. Mater. Lett., 2024, 356, 1335594: 1-4. https://doi.org/10.1016/j.matlet.2023.135594. |
| [18] | Madec L, Ma L, Nelson K J, Petibon R, Sun J-P, Hill I G, Dahn J R. The effects of a ternary electrolyte additive system on the electrode/electrolyte interfaces in high voltage Li-ion cells[J]. J. Electrochem. Soc., 2016, 163(6): A1001-A1009. https://doi.org/10.1149/2.1051606jes. |
| [19] | Dominko R, Goupil J M, Bele M, Gaberscek M, Remskar M, Hanzel D, Jamnik J. Impact of LiFePO4/C composites porosity on their electrochemical performance[J]. J. Electrochem. Soc., 2005, 152(5): A858-A863. https://doi.org/10.1149/1.1872674. |
| [20] | Hu Y G, Liang J D, Chen X X, Chen G K, Peng Y F, Tang S J, He Z F, Li D J, Zhang Z R, Gong Z L, Wei Y M, Yang Y. Comparative study of thermodynamic & kinetic parameters measuring techniques in lithium-ion batteries[J]. J. Power Sources, 2024, 606: 234590-234605. https://doi.org/10.1016/j.jpowsour.2024.234590. |
| [21] | Qin G X, Zhang J L, Chen H B, Li H, Hu J, Chen Q, Hou G Y, Tang Y P. Lithium difluoro (oxalate) borate as electrolyte additive to form uniform, stable and LiF-rich solid electrolyte interphase for high performance lithium ion batteries[J]. Surf. Interfaces, 2024, 48, 104297: 1-9. https://doi.org/10.1016/j.surfin.2024.104297. |
| [22] | Lei Y, Xu X, Yin J Y, Xu Z F, Wei L, Zhu X Q, Pan L N, Jiang S, Gao Y F. Regulating Li-ion solvation structure and electrode-electrolyte interphases via triple-functional electrolyte additive for lithium-metal batteries[J]. Chem. Eng. J., 2024, 497: 154927-154938. https://doi.org/10.1016/j.cej.2024.154927. |
| [23] | Han F J, Chang Z H, Wang R N, Yun F L, Wang J, Ma C X, Zhang Y, Tang L, Ding H Y, Lu S G. Isocyanate additives improve the low-temperature performance of LiNi0.8Mn0.1Co0.1O2||SiOx@Graphite Lithium-Ion Batteries[J]. ACS Appl. Mater. Interfaces, 2023, 15(17): 20966-20976. https://doi.org/10.1021/acsami.3c00554. |
/
| 〈 |
|
〉 |
