锂离子电池正极材料原位漫反射光谱电化学研究

doi:10.61558/2993-074X.3446

摘要/Abstract

摘要：

发展原位电化学光谱方法对深入研究电化学反应机理，并最终提高电池性能有着重要价值。建立在这一认识之上，能够应用于电池体系的原位光谱电化学表征技术被认为是表征电池电极材料性能的有效方法。但是受限于电池严格密封的不透明外壳和当前商用电池体系严格隔绝水氧的客观要求，开发更贴近真实电池工作条件的原位光谱电化学表征技术仍有较大需求。基于此，本文设计了一种基于传统纽扣电池架构的原位电化学池，该装置通过特殊设计实现了在尽可能模拟电池工作环境的前提下拥有透明的上盖，从而使发生电化学反应的同时进行光学检测成为可能。利用这一电化学池，本文以锂离子电池中常用的正极材料LiFePO₄(LFP)、NCM811和LiCoO₂(LCO)为例，对其电化学反应过程中的漫反射光谱进行了采集和分析。相关数据定量地揭示了不同种类电极材料在一般反射光路架构下对不同波长可见光的响应关系，并能够直接用于对单色光检测场景下的波长优化提供指导和依据。更进一步，本文还对不同材料在充放电过程中的光谱特征进行了定量分析，揭示了其光谱特征同材料内在能级状态间的相关性。综上，本文提出了一种基于漫反射光谱的原位光谱电化学表征方法，作为对光谱电化学应用于电池体系的有效补充，本方法能够为评估电极材料性能提供一种全新且简单直接的途径，并最终助力电池性能的提升。

关键词: 锂离子电池, 漫反射光谱电化学, 原位, 正极材料

Abstract:

Developing in situ spectroelectrochemistry methods, which can provide detailed information about species transformation during electrochemical reactions, is very important for studying electrode reaction mechanisms and improving battery performance. Studying real-time changes in the surface of electrode materials during normal operation can be an effective way to assess and optimize the practical performance of electrode materials, thus, in situ and in operando characterization techniques are particularly important. However, batteries are hard to be studied by in situ characterization measurements due to their hermetically sealed shells, and there is still much room for battery characterizations. In this work, a specially designed battery based on the structure of coin cells, whose upper cover was transparent, was constructed. With such a device, acquisition of diffuse reflectance spectra of electrode materials during charging and discharging was realized. This not only provided a simple measurement accessory for diffuse reflectance spectroscopy (DRS), but also complemented in situ characterization techniques for batteries. Taking commonly used cathode materials in lithium-ion batteries (LIBs), including LiFePO₄ (LFP), NCM811 and LiCoO₂ (LCO) as examples, we managed to find out the response relationships of different electrode materials to visible light of different wavelengths under ordinary reflectance illumination conditions. Heterogeneity of different cathode materials on interaction relationships with the lights of different wavelengths was also revealed. This work demonstrated the capability of guiding wavelength selection for different materials and assessing electrochemical performances of in situ diffuse reflectance spectroelectrochemistry. By combining electrochemistry with diffuse reflectance spectroscopy, this work made an effective complementary for spectroelectrochemistry.

Key words: Lithium-ion battery, Diffuse reflectance spectroelectrochemistry, In situ, Cathode material

陈露露, 李浩冉, 刘维祎, 王伟. 锂离子电池正极材料原位漫反射光谱电化学研究[J]. 电化学（中英文）, 2024, 30(6): 2314006.

Lu-Lu Chen, Hao-Ran Li, Wei-Yi Liu, Wei Wang. In situ Diffuse Reflectance Spectroelectrochemistry of Cathode Materials in Lithium-Ion Batteries[J]. Journal of Electrochemistry, 2024, 30(6): 2314006.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.61558/2993-074X.3446

https://electrochem.xmu.edu.cn/CN/Y2024/V30/I6/2314006

图/表 4

参考文献 23

[1]	Degen F, Winter M, Bendig D, Tübke J. Energy consumption of current and future production of lithium-ion and post lithium-ion battery cells[J]. Nat. Energy, 2023, 8(11): 1284-1295.
[2]	Zhao L, Hu Y S, Li H, Wang Z X, Xu H X, Huang X J, Chen L Q. Applications of Raman spectroscopy technique in lithium ion batteries[J]. J. Electrochem., 2011, 17(1): 12-23.
[3]	Ren B, Li J F, Huang Y F, Zeng Z C, Tian Z Q. Electrochemical surface-enhanced Raman spectroscopy—current status and perspective[J]. J. Electrochem., 2010, 16(3): 305-316.
[4]	Li W J, Zheng J Y, Gu L, Li H. Researches on in-situ and ex-situ characterization techniques in lithium batteries[J]. J. Electrochem., 2015, 21(2): 99-114.
[5]	Li H R, Wang W. Recent advances of in situ and in operando optical imaging techniques for battery researches[J]. Curr. Opin. Electrochem., 2023, 41: 101376.
[6]	Elgrishi N, Rountree K J, McCarthy B D, Rountree E S, Eisenhart T T, Dempsey J L. A practical beginner’s guide to cyclic voltammetry[J]. J. Chem. Educ., 2018, 95(2): 197-206.
[7]	Liu H N, Naqvi I H, Li F J, Liu C L, Shafiei N, Li Y L, Pecht M. An analytical model for the CC-CV charge of Li-ion batteries with application to degradation analysis[J]. J. Energy Storage, 2020, 29: 101342.
[8]	Wang J, Huang Q A, Li W H, Wang J, Zhuang Q C, Zhang J J. Fundamentals of distribution of relaxation times for electrochemical impedance spectroscopy[J]. J. Electrochem., 2020, 26(5): 607-627. doi: 10.13208/j.electrochem.200641
[9]	Kaim W, Fiedler J. Spectroelectrochemistry: the best of two worlds[J]. Chem. Soc. Rev., 2009, 38(12): 3373-3382. doi: 10.1039/b504286k pmid: 20449056
[10]	Lozeman J J A, Führer P, Olthuis W, Odijk M. Spectroelectrochemistry, the future of visualizing electrode processes by hyphenating electrochemistry with spectroscopic techniques[J]. Analyst, 2020, 145(7): 2482-2509. doi: 10.1039/c9an02105a pmid: 31998878
[11]	Zhang D Z, Wang R C, Wang X H, Gogotsi Y. In situ monitoring redox processes in energy storage using UV-Vis spectroscopy[J]. Nat. Energy, 2023, 8(6): 567-576.
[12]	Edwards P, Zhang C J, Zhang B G, Hong X Q, Nagarajan V K, Yu B, Liu Z W. Smartphone based optical spectrometer for diffusive reflectance spectroscopic measurement of hemoglobin[J]. Sci. Rep., 2017, 7(1): 12224. doi: 10.1038/s41598-017-12482-5 pmid: 28939898
[13]	Liu H F, Guo B G, Wang L, Xie R S, Yang J C, Li J, Zhang X Q, Zheng K, Huo J C. Adjusting the photoconductive properties of LaCoO₃ thin films by epitaxial strain[J]. Opt. Mater., 2021, 121: 111537.
[14]	Pandya R, Valzania L, Dorchies F, Xia F, Mc Hugh J, Mathieson A, Tan H J, Parton T G, Godeffroy L, Mazloomian K, Miller T S, Kanoufi F, Volder M D, Tarascon J, Gigan S, Aguiar H B, Grimaud A. Three-dimensional operando optical imaging of particle and electrolyte heterogeneities inside Li-ion batteries[J]. Nat. Nanotechnol., 2023, 18(10): 1185-1194.
[15]	Liu Y S, Sun Q, Yang X F, Liang J N, Wang B Q, Koo A, Li R Y, Li J, Sun X L. High-performance and recyclable Al-air coin cells based on eco-friendly chitosan hydrogel membranes[J]. ACS Appl. Mater. Interfaces, 2018, 10(23): 19730-19738.
[16]	Xu C J, Dai Q, Gaines L, Hu M M, Tukker A, Steubing B. Future material demand for automotive lithium-based batteries[J]. Commun. Mater., 2020, 1(1): 99.
[17]	Barbosa J C, Gonçalves R, Costa C M, Lanceros-Méndez S. Toward sustainable solid polymer electrolytes for lithium-ion batteries[J]. ACS Omega, 2022, 7(17): 14457-14464. doi: 10.1021/acsomega.2c01926 pmid: 35572743
[18]	Zhang J N, Li Q H, Ouyang C Y, Yu X Q, Ge M Y, Huang X J, Hu E Y, Ma C, Li S F, Xiao R J, Yang W L, Chu Y, Liu Y J, Yu H G, Yang X Q, Huang X J, Chen L Q, Li H. Trace doping of multiple elements enables stable battery cycling of LiCoO₂ at 4.6 V[J]. Nat. Energy, 2019, 4(7): 594-603.
[19]	Wang J Y, Wang R, Wang S Q, Wang Y F, Zhan C. Facile one-step solid-state synthesis of Ni-rich layered oxide cathodes for lithium-ion batteries[J]. J. Electrochem., 2022, 28(8): 2112131.
[20]	Wei X F, Guan Y B, Zheng X H, Zhu Q Z, Shen J R, Qiao N, Zhou S Q, Xu B. Improvement on high rate performance of LiFePO₄ cathodes using graphene as a conductive agent[J]. Appl. Surf. Sci., 2018, 440: 748-754.
[21]	Wang W. Imaging the chemical activity of single nanoparticles with optical microscopy[J]. Chem. Soc. Rev., 2018, 47(7): 2485-2508. doi: 10.1039/c7cs00451f pmid: 29542749
[22]	Lu J H, Xiong R, Tian J P, Wang C X, Sun F C. Deep learning to estimate lithium-ion battery state of health without additional degradation experiments[J]. Nat. Commun., 2023, 14(1): 2760. doi: 10.1038/s41467-023-38458-w pmid: 37179411
[23]	Zhang Y, Alarco J A, Best A S, Snook G A, Talbot P C, Nerkar J Y. Re-evaluation of experimental measurements for the validation of electronic band structure calculations for LiFePO₄ and FePO₄[J]. RSC Adv., 2019, 9(2): 1134-1146. doi: 10.1039/c8ra09154d