铜取代型Li2Ni1-xCuxO2正极补锂剂提升石墨/磷酸铁锂电池循环寿命

doi:10.61558/2993-074X.3515

摘要/Abstract

摘要：

镍酸锂（Li₂NiO₂）作为一种正极补锂剂，用于补偿锂离子损失，以提高锂离子电池的循环寿命。然而，Li₂NiO₂补锂剂存在成本高、脱锂动力学较差的问题。本文研究了基于高温固相法合成的低成本铜（Cu）取代型Li₂Ni_1-_xCu_xO₂（x = 0, 0.2, 0.3, 0.5, 0.7）补锂剂对石墨/磷酸铁锂电池结构、形貌和电化学性能的影响。晶体结构精修结果表明，Cu取代策略有利于消除NiO_x杂质相，弱化Li-O键。理论计算结果显示Cu取代可提高补锂剂电子电导率。同时，电化学分析证实Cu取代有利于降低脱锂电位，提高脱锂容量。其中，最优比例的Li₂Ni_0.7Cu_0.3O₂具有437 mAh·g^-1的高脱锂容量，较Li₂NiO₂提升约8%。此外，设计了容量为3000 mAh的石墨/磷酸铁锂软包电池，采用2 wt% Li₂Ni_0.7Cu_0.3O₂补锂剂，其1000次循环的可逆容量、能量密度和循环寿命显著提高；其首圈放电容量提升6.2 mAh·g^-1，0.5 P循环1000圈容量保持率提升约5%。对循环后的电池进行拆解分析后发现Li₂Ni_0.7Cu_0.3O₂添加剂可以减少固体电解质界面（SEI）的分解、改善脱嵌锂的均一性，从而提高石墨负极与电解液之间的界面稳定性，抑制析锂。综上，与Li₂NiO₂相比，Li₂Ni_0.7Cu_0.3O₂具有成本低、脱锂电压低和预锂化容量高的优点，是极具前景的下一代锂离子电池正极补锂剂材料。

关键词: Li₂Ni_1-_xCu_xO₂, 正极补锂剂, 磷酸铁锂电池, 循环寿命, 电网储能

Abstract:

Lithium nickel oxide (Li₂NiO₂), as a sacrificial cathode prelithiation additive, has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries (LIBs). However, high-cost Li₂NiO₂ suffers from inferior delithiation kinetics during the first cycle. Herein, we investigated the effects of the cost-effective copper substituted Li₂Ni_1-xCu_xO₂ (x = 0, 0.2, 0.3, 0.5, 0.7) synthesized by a high-temperature solid-phase method on the structure, morphology, electrochemical performance of graphite‖LiFePO₄ battery. The X-ray diffraction (XRD) refinement result demonstrated that Cu substitution strategy could be favorable for eliminating the NiO_x impurity phase and weakening Li-O bond. Analysis on density of states (DOS) indicates that Cu substitution is good for enhancing the electronic conductivity, as well as reducing the delithiation voltage polarization confirmed by electrochemical characterizations. Therefore, the optimal Li₂Ni_0.7Cu_0.3O₂ delivered a high delithiation capacity of 437 mAh·g^-1, around 8% above that of the pristine Li₂NiO₂. Furthermore, a graphite‖LiFePO₄ pouch cell with a nominal capacity of 3000 mAh demonstrated a notably improved reversible capacity, energy density and cycle life through introducing 2 wt% Li₂Ni_0.7Cu_0.3O₂ additive, delivering a 6.2 mAh·g^-1 higher initial discharge capacity and achieving around 5% improvement in capacity retentnion at 0.5P over 1000 cycles. Additionally, the post-mortem analyses testified that the Li₂Ni_0.7Cu_0.3O₂additive could suppress solid electrolyte interphase (SEI) decomposition and homogenize the Li distribution, which benefits to stabilizing interface between graphite and electrolyte, and alleviating dendritic Li plating. In conclusion, the Li₂Ni_0.7Cu_0.3O₂additive may offer advantages such as lower cost, lower delithiation voltage and higher prelithiation capacity compared with Li₂NiO₂, making it a promising candidate of cathode prelithiation additive for next-generation LIBs.

Key words: Li₂Ni_1-xCu_xO₂, cathode prelithiation additive, LiFePO₄ battery, cycle life, grid energy storage

郑建明, 张静文, 焦天鹏. 铜取代型Li₂Ni_1-_xCu_xO₂正极补锂剂提升石墨/磷酸铁锂电池循环寿命[J]. 电化学（中英文）, 2025, 31(2): 2408301.

Jian-Ming Zheng, Jing-Wen Zhang, Tian-Peng Jiao. Enhancing Cycle Life of Graphite‖LiFePO₄ Batteries via Copper Substituted Li₂Ni_1-_xCu_xO₂ Cathode Prelithiation Additive[J]. Journal of Electrochemistry, 2025, 31(2): 2408301.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3515

https://electrochem.xmu.edu.cn/CN/Y2025/V31/I2/2408301

图/表 6

参考文献 34

[1]	Kebede A A, Kalogiannis T, Van Mierlo J, Berecibar M. A comprehensive review of stationary energy storage devices for large scale renewable energy sources grid integration[J]. Renew. Sust. Energ. Rev., 2022, 159: 112213.
[2]	Huang X, Luo B, Chen P, Searles D J, Wang D, Wang L Z. Sulfur-based redox chemistry for electrochemical energy storage[J]. Coord. Chem. Rev., 2020, 422: 213445.
[3]	Chen H S, Cong T N, Yang W, Tan C Q, Li Y L, Ding Y L. Progress in electrical energy storage system: A critical review[J]. Prog. Nat. Sci., 2009, 19(3): 291-312.
[4]	Tian Y S, Zeng G B, Rutt, A, Shi T, Kim H, Wang J Y, Koettgen J, Sun Y Z, Ouyang B, Chen T, Lun Z Y, Rong Z Q, Persson K, Ceder G. Promises and challenges of next-generation "beyond Li-ion" batteries for electric vehicles and grid decarbonization[J]. Chem. Rev., 2021, 121 (3): 1623-1669. doi: 10.1021/acs.chemrev.0c00767 pmid: 33356176
[5]	Yang Z G, Dai Y, Wang S P, Yu J X. How to make lithium iron phosphate better: a review exploring classical modification approaches in-depth and proposing future optimization methods[J]. J. Mater. Chem. A., 2016, 4(47): 18210-18222.
[6]	Shi Z C, Li C, Yang Y. The electrochemical performance studies on novel LiFePO₄ cathode materials for Li-ion batteries[J]. J. Electrochem., 2003, 9(1): 9-14.
[7]	Xie H, Zhou Z H. The synthesis, structure and electrochemical performances of lithium iron phosphate[J]. J. Electrochem., 2006, 12(4): 378-381.
[8]	Niu J T, Sun L, Kang S W, Zhao Z W, Ma Z F. Impact of water content on the performance of LiFePO₄ based lithium-ion battery[J]. J. Electrochem., 2015, 21(5): 465-470.
[9]	Peng Y F, Zhong C, Ding M F, Zhang H Y, Jin Y T, Hu Y G, Liao Y Q, Yang L F, Wang S X, Yin X T, Liang J D, Wei Y M, Chen J, Yan J W, Wang X F, Gong Z L, Yang Y. Quantitative analysis of active lithium loss and degradation mechanism in temperature accelerated aging process of lithium-ion batteries[J]. Adv. Funct. Mater., 2024, 34(42): 2404495.
[10]	Holtstiege F, Wilken A, Winter M, Placke T. Running out of lithium? A route to differentiate between capacity losses and active lithium losses in lithium-ion batteries[J]. Phys. Chem. Chem. Phys., 2017, 19(38), 25905-25918. doi: 10.1039/c7cp05405j pmid: 28926044
[11]	Wang Cun, Zhang W J, He T F, Lei B, Shi Y J, Zhang Y D, Luo W L, Jiang F M. Degradation and thermal characteristics of LiNi_0.8Co_0.15Al_0.05O₂/Graphite lithium ion battery after different state of charge ranges cycling[J]. J. Electrochem., 2020, 26(6): 777-788.
[12]	Lang S Y, Shen Z Z, Hu X C, Shi Y, Guo Y G, Jia F F, Wang F Y, Wen R, Wan L J. Tunable structure and dynamics of solid electrolyte interphase at lithium metal anode[J]. Nano Energy., 2020, 75: 104967.
[13]	Cheng X B, Hou T Z, Zhang R, Peng H J, Zhao C Z, Huang J Q, Zhang Q. Dendrite-free lithium deposition induced by uniformly distributed lithium ions for efficient lithium metal batteries[J]. Adv. Mater., 2016, 28(15): 2888-2895.
[14]	Zou K Y, Deng W T, Cai P, Deng X L, Wang B W, Liu C, Li J Y, Hou H S, Zou G Q, Ji X B. Prelithiation/presodiation techniques for advanced electrochemical energy storage systems: concepts, applications, and perspectives[J]. Adv. Funct. Mater., 2020, 31(5): 2005581.
[15]	Sun Y M, Lee H W, Seh Z W, Liu N, Sun J, Li Y Z, Cui Y. High-capacity battery cathode prelithiation to offset initial lithium loss[J]. Nat. Energy, 2016, 1(1): 15008.
[16]	Li Z, Sun X Z, Liu W J, Zhang X, Wang K, Ma Y W. A comparative study of pre-lithiated hard carbon and soft carbon as anodes for lithium-ion capacitors[J]. J. Electrochem., 2019, 25(1): 122-136. doi: 10.13208/j.electrochem.180306
[17]	Yue X Y, Yao Y X, Zhang J, Yang S Y, Li Z H, Yan C, Zhang Q. Unblocked electron channels enable efficient contact prelithiation for lithium-ion batteries[J]. Adv. Mater., 2022, 34(15): 2110337.
[18]	Cao Z Y, Xu P Y, Zhai H W, Du S C, Mandal J, Dontigny M, Zaghib K, Yang Y. Ambient-air stable lithiated anode for rechargeable Li-ion batteries with high energy density[J]. Nano Lett., 2016, 16(11): 7235-7240. pmid: 27696883
[19]	Wu Z C, Li R H, Zhang S Q, Lv L, Deng T, Zhang H, Zhang R X, Liu J J, Ding S H, Fan L W, Chen L X, Fan X L. Deciphering and modulating energetics of solvation structure enables aggressive high-voltage chemistry of Li metal batteries[J]. Chem, 2023, 9(3): 650-664.
[20]	Zhong W, Zeng Z Q, Cheng S J, Xie J. Advancements in prelithiation technology: transforming batteries from Li-shortage to Li-rich systems[J]. Adv. Funct. Mater., 2023, 34(2): 2307860.
[21]	Liu X M, Wu Z, Xie L Q, Sheng L, Liu J H, Wang L, Wu K, He X M. Prelithiation enhances cycling life of lithium-ion batteries: a mini review[J]. Energy Environ. Mater., 2023, 6(6): e12501.
[22]	Fu Y P, Xie Y, Zeng L Y, Shi Z C. Li₂Se as cathode additive to prolong the next generation high energy lithium-ion batteries[J]. Surf. Interfaces, 2023, 36: 102610.
[23]	Pan Y J, Qi X Q, Du H R, Ji Y S, Yang D, Zhu Z L, Yang Y, Qie L, Huang Y H. Li₂Se as a cathode prelithiation additive for lithium-ion batteries[J]. ACS Appl. Mater. Interfaces, 2023, 15(15), 18763-18770.
[24]	Zhan R M, Wang X C, Chen Z H, Seh Z W, Wang L, Sun Y M. Promises and challenges of the practical implementation of prelithiation in lithium-ion batteries[J]. Adv. Energy Mater., 2021, 11 (35): 2101565.
[25]	Back C K, Yin R-Z, Shin S-J, Lee Y-S, Choi W, Kim Y S. Electrochemical properties and gas evolution behavior of overlithiated Li₂NiO₂ as cathode active mass for rechargeable Li ion batteries[J]. J. Electrochem. Soc., 2012, 159 (6): A887-A893.
[26]	Kim M G, Cho J. Air stable Al₂O₃-coated Li₂NiO₂cathode additive as a surplus current consumer in a Li-ion cell[J]. J. Mater. Chem., 2008, 18(48): 5880-5887.
[27]	Han H, Go C Y, Kim K C. Dopant-based modulation of structural, electronic, and electrochemical properties of Li-excessive Li₂NiO₂ cathodes[J]. Curr. Appl. Phys., 2023, 48, 1-10.
[28]	Yue X Y, Yao Y X, Zhang J, Li Z H, Yang S Y, Li X L, Yan C, Zhang Q. The raw mixed conducting interphase affords effective prelithiation in working batteries[J]. Angew. Chem. Int. Ed., 2022, 61(29): e202205697.
[29]	Lee H, Chang S K, Goh E Y, Jeong J Y, Lee J H, Kim H J, Cho J J, Hong S T. Li₂NiO₂ as a novel cathode additive for overdischarge protection of Li-ion batteries[J]. Chem. Mater., 2008, 20, 1, 5-7.
[30]	Wu Y L, Zhang W, Li S H, Wen N F, Zheng J Q, Zhang L Y, Zhang Z A, Lai Y Q. Li₂Cu_0.1Ni_0.9O₂ with copper substitution: a new cathode prelithiation additive for lithium-ion batteries[J]. ACS Sustainable Chem. Eng., 2023, 11: 1044-1053.
[31]	Biesinger M C. Accessing the robustness of adventitious carbon for charge referencing (correction) purposes in XPS analysis: Insights from a multi-user facility data review[J]. Appl. Surf. Sci., 2022, 597: 153681.
[32]	Sun H, Zhu G Z, Zhu Y M, Lin M C, Chen H, Li Y Y, Hung W H, Zhou B, Wang X, Bai Y X, Gu M, Huang C L, Tai H C, Xu X T, Angell M, Shyue J J, Dai H J. High-safety and high-energy-density lithium metal batteries in a novel ionic-liquid electrolyte[J]. Adv. Mater., 2020, 32(26): 2001741.
[33]	Katayama M, Sumiwaka K, Miyahara R, Yamashige H, Arai H, Uchimoto Y, Ohta T, Inada Y, Ogumi Z. X-ray absorption fine structure imaging of inhomogeneous electrode reaction in LiFePO4 lithium-ion battery cathode[J]. J. Power Sources, 2014, 269: 994-999.
[34]	Liu T C, Lin L P, Bi X X, Tian L L, Yang K, Liu J J, Li M F, Chen Z H, Lu J, Amine K, Xu K, Pan F. In situ quantification of interphasial chemistry in Li-ion battery[J]. Nat. Nanotechnol., 2019, 14: 50-56. doi: 10.1038/s41565-018-0284-y pmid: 30420761

铜取代型Li₂Ni_1-_xCu_xO₂正极补锂剂提升石墨/磷酸铁锂电池循环寿命

Enhancing Cycle Life of Graphite‖LiFePO₄ Batteries via Copper Substituted Li₂Ni_1-_xCu_xO₂ Cathode Prelithiation Additive

RichHTML

PDF (PC)

补充材料

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 34

相关文章 5

Metrics

[1]	马世花, 尹起, 赵金平. 电解质杂化效应衍生的高性能水系超级电容器[J]. 电化学（中英文）, 2024, 30(11): 2408051-.
[2]	陈品松, 胡一涛, 张信义, 沈培康. 立体构造石墨烯材料对铅酸蓄电池负极性能影响的研究[J]. 电化学（中英文）, 2020, 26(6): 834-843.
[3]	郭择良，伍晖. 锂离子电池硅负极循环稳定性研究进展[J]. 电化学（中英文）, 2016, 22(5): 499-512.
[4]	张海昌, 檀立新, 呙成, 明文成, 任学颖. 电化学浸渍法制备空间氢镍电池用镍电极的循环寿命研究[J]. 电化学（中英文）, 2012, 18(1): 84-88.
[5]	杨书廷,尹艳红,陈红军,贾俊华,张明春,丁立. 不同镍盐合成的球形β-Ni(OH)_2的充放电特性与结构变化规律[J]. 电化学（中英文）, 2001, 7(3): 310-315.