锂电池研究中的拉曼/红外实验测量和分析方法

doi:10.12028/j.issn.2095-4239.2019.0082

摘要/Abstract

摘要： 拉曼光谱和傅里叶变换红外光谱是重要的物理表征方法，在电化学领域尤其是锂电池领域具有广泛的应用，常用于分析分子价键、官能团振动和转动能级跃迁状态、物相结构变化、稳定性、表面现象以及反应机理，相关谱学数据又可以计算化学键的键能、键长、键角等。本文介绍了拉曼和红外光谱的基本原理、测试方法、测试注意事项、常用测试设备及测试流程，并结合实际案例，具体分析了拉曼和红外光谱在锂电池电极材料、电解质、黏结剂等组分分析方面，及其在充放电循环中的生成产物对电化学稳定性的影响方面的应用研究。

关键词: 拉曼光谱, 傅里叶变换红外光谱, 测试方法, 分析方法, 锂电池

Abstract: Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR) are important physical characterization methods. They are widely used in the field of electrochemistry, especially in the field of lithium batteries. They are commonly used to analyze molecular valence bonds, functional group vibration and rotational energy level transition states, phase structure changes, stability, surface phenomena and reaction mechanism, the correlation spectroscopy data can calculate the bond energy, bond length, bond angle, etc. of the chemical bond. This paper introduces the basic principles, test methods, test precautions, common test equipment and test procedures of Raman and infrared spectroscopy, and analyzes Raman and infrared spectroscopy in lithium battery electrode materials, electrolytes and binders. The application of isocomponent analysis and its influence on the electrochemical stability of the product formed in the charge and discharge cycle.

Key words: Raman spectroscopy, Fourier transform infrared spectroscopy, test methods, analysis methods, lithium batteries

中图分类号:

O657.3

孙姝纬, 赵慧玲, 郁彩艳, 白莹. 锂电池研究中的拉曼/红外实验测量和分析方法[J]. 储能科学与技术, 2019, 8(5): 975-996.

SUN Shuwei, ZHAO Huiling, YU Caiyan, BAI Ying. Experimental measurement and analysis of Raman/infrared methods for lithium batteries[J]. Energy Storage Science and Technology, 2019, 8(5): 975-996.

参考文献

[1] 张树霖. 拉曼光谱学与低维纳米半导体[M]. 北京:科学出版社, 2008. ZHANG S L. Raman spectroscopy and low-dimensional nanosemiconductors[M]. Beijing:Science Press, 2008.
[2] 黄可龙, 王兆翔, 刘素琴. 锂离子电池原理与关键技术[M]. 北京:化学工业出版社, 2007. HUANG K L, WANG Z X, LIU S Q. Principle and key technology of lithium ion battery[M]. Beijing:Chemical Industry Press, 2007.
[3] 李文俊, 褚赓, 彭佳悦, 等. 锂离子电池基础科学问题(Ⅻ)——表征方法[J]. 储能科学与技术, 2014, 3(6):642-667. LI W J, CHU G, PENG J Y, et al. Fundamental scientific aspects of lithium batteries(Ⅻ)-Characterization techniques[J]. Energy Storage Science and Technology, 2014, 3(6):642-667.
[4] 李琼瑶. FTIR和Raman光谱技术的进展[J]. 现代科学仪器, 2000, 3(1):40-42. LI Q Y. Advances in FTIR and Raman spectral techniques[J]. Modern Scientific Instruments, 2000, 3(1):40-42.
[5] NOVAK P, PANITZ J C, JOHO F, et al. Advanced in situ methods for the characterization of practical electrodes in lithium-ion batteries[J]. J. Power Sources, 2000, 90(1):52-58.
[6] JULIEN C M. Lithium intercalated compounds charge transfer and related properties[J]. Materials Science and Engineering R, 2003, 40(2):47-102.
[7] DING Y L, XIE J, CAO G S, et al. Single-crystalline LiMn₂O₄ nanotubes synthesized via template-engaged reaction as cathodes for high-power lithium ion batteries[J]. Adv. Funct. Mater., 2011, 21(2):348-355.
[8] DOEFF M M, HU Y Q, MCLARNON F, et al. Effect of surface carbon structure on the electrochemical performance of LiFePO₄[J]. Electrochem. Solid-State Lett., 2003, 6(10):A207-A209.
[9] DUAN W C, HU Z, ZHANG K, et al. Li₃V₂(PO₄)₃@C core-shell nanocomposite as a superior cathode material for lithium-ion batteries[J]. Nanoscale, 2013, 5(14):6485-6490.
[10] OKUBO M, HOSONO E, KIM J, et al. Nanosize effect on high-rate Li-ion intercalation in LiCoO₂ electrode[J]. J. Am. Chem. Soc., 2007, 129(23):7444-7452.
[11] LIANG X, SERGUEI V S, VALERY V L, et al. Self-standing porous LiCoO₂ nanosheet arrays as 3D cathodes for flexible Li-ion batteries[J]. Adv. Funct. Mater., 2018, 28(7):doi:10.1002/adfm.201705836.
[12] AMDOUNI N, ZAGHIB K, GENDRON F, et al. Structure and insertion properties of disordered and ordered LiNi_0.5Mn_1.5O₄ spinels prepared by wet chemistry[J]. Ionics, 2006, 12(2):117-126.
[13] WANG L P, LI H, HUANG X J, et al. A comparative study of Fd-3m and P4₃32 "LiNi_0.5Mn_1.5O₄"[J]. Solid State Ionics, 2011, 193(1):32-38.
[14] SONG B, LAI M O, LIU Z W, et al. Graphene-based surface modification on layered Li-rich cathode for high-performance Li-ion batteries[J]. J. Mater. Chem. A, 2013, 1(34):9954-9965.
[15] ZHAO J Q, HUANG R M, GAO W P, et al. An ion-exchange promoted phase transition in a Li-excess layered cathode material for highperformance lithium ion batteries[J]. Adv. Energy Mater., 2015, 5(9):doi:10.1002/aenm.201401937.
[16] REDDY A, SRIVASTAVA A, GOWDA S R, et al. Synthesis of nitrogen-doped graphene films for lithium battery application[J]. ACS Nano, 2010, 4(11):6337-6342.
[17] MAO Y, DUAN H, XU B, et al. Lithium storage in nitrogen-rich mesoporous carbon materials[J]. Energy Environ. Sci., 2012, 5(7):7950-7955.
[18] ZHANG Z L, WANG Y H, REN W F, et al. Scalable synthesis of interconnected porous silicon/carbon composites by the rochow reaction as high-performance anodes of lithium ion batteries[J]. Angew. Chem. Int. Ed., 2014, 53(20):5165-5169.
[19] LI H, HUANG X J, CHEN L Q, et al. The crystal structural evolution of nano-Si anode caused by lithium insertion and extraction at room temperature[J]. Solid State Ionics, 2000, 135(4):181-191.
[20] KAVAN L, KALBAC M, ZUKALOVA M, et al. Lithium storage in nanostructured TiO₂ made by hydrothermal growth[J]. Chem. Mater., 2004, 16(3):477-485.
[21] BRUTTI S, GENTILI V, MENARD H, et al. TiO₂-(B) Nanotubes as anodes for lithium batteries:Origin and mitigation of irreversible capacity[J]. Adv. Energy Mater., 2012, 2(3):322-327.
[22] LI F H, SONG J F, YANG H F, et al. One-step synthesis of graphene/SnO₂ nanocomposites and its application in electrochemical supercapacitors[J]. Nanotechnology, 2009, 20(45):doi:10.1021/am201541s.
[23] AURBACH D, GAMOLSKY K, MARKOVSKY B, et al. The study of surface phenomena related to electrochemical lithium intercalation into Li xMOy host materials (M=Ni, Mn)[J]. J. Electrochem. Soc., 2000, 147(4):1322-1331.
[24] WANG Z X, GAO W D, HUANG X J, et al. Spectroscopic studies on interactions and microstructures in propylene carbonate-LiTFSI electrolytes[J]. J. Raman Spectrosc., 2001, 32(11):900-905.
[25] ZHUANG G R, XU K, YANG H, et al. Lithium ethylene dicarbonate identified as the primary product of chemical and electrochemical reduction of EC in 1.2 M LiPF 6/EC:EMC electrolyte[J]. J. Phys. Chem. B, 2005, 109(37):17567-17573.
[26] LIU H J, TONG Y J, KUWATA N, et al. Adsorption of propylene carbonate (PC) on the LiCoO₂ surface investigated by nonlinear vibrational spectroscopy[J]. J. Phys. Chem. C, 2009, 113(48):20531-20534.
[27] YU L, LIU H J, WANG Y, et al. Preferential adsorption of solvents on the cathode surface of lithium ion batteries[J]. Angew. Chem. Int. Ed., 2013, 52(22):5753-5756.
[28] MCCLOSKEY B D, BETHUNE D S, SHELBY R M, et al. Solvents' critical role in nonaqueous lithium-oxygen battery electrochemistry[J]. J. Phys. Chem. Lett., 2011, 2(10):1161-1166.
[29] NORBERG N S, LUX S F, KOSTECKI R. Interfacial side-reactions at a LiNi_0.5Mn_1.5O₄ electrode in organic carbonate-based electrolytes[J]. Electrochem. Commun., 2013, 34(1):29-32.
[30] SUO L M, BORODIN O, GAO T, et al. "Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries[J]. Science, 2015, 350(6263):938-943.
[31] MARKEVICH E, SALITRA G, CHESNEAU F, et al. Very stable lithium metal stripping-plating at a high rate and high areal capacity in fluoroethylene carbonate-based organic electrolyte solution[J]. ACS Energy Lett., 2017, 2(6):1321-1326.
[32] ZHUANG G V, YANG H, ROSS P N, et al. Lithium methyl carbonate as a reaction product of metallic lithium and dimethyl carbonate[J]. Electrochem. Solid-State Lett., 2006, 9(2):A64-A68.
[33] SANTNER H J, KOREPP C, WINTER M, et al. In-situ FTIR investigations on the reduction of vinylene electrolyte additives suitable for use in lithium-ion batteries[J]. Anal. Bioanal. Chem., 2004, 379(2):266-271.
[34] CORTE D, CAILLON G, JORDY C, et al. Spectroscopic insight into Li-ion batteries during operation:an alternative infrared approach[J]. Adv. Energy Mater., 2016, 6(2):doi:10.1002/aenm.201501768.
[35] MAAZI S, NAVARCHIAN A H, KHOSRAVI M, et al. Effect of poly (vinylidene fluoride)/poly (vinyl acetate) blend composition as cathode binder on electrochemical performances of aqueous Li-ion battery[J]. Solid State Ionics, 2018, 320(1):84-91.
[36] GAO S Y, SU Y F, BAO L Y, et al. High-performance LiFePO₄/C electrode with polytetrafluoroethylene as an aqueous-based binder[J]. J. Power Sources, 2015, 298(1):292-298.
[37] HAREGEWOIN A M, TERBORG L, ZHANG L, et al. The electrochemical behavior of poly 1-pyrenemethyl methacrylate binder and its effect on the interfacial chemistry of a silicon electrode[J]. J. Power Sources, 2018, 376(1):152-160.
[38] MARKEVICH E, SALITRA G, AURBACH D. Influence of the PVDF binder on the stability of LiCoO₂ electrodes[J]. Electrochem. Commun., 2005, 7(12):1298-1304.
[39] VOGL U S, DAS P K, WEBER A Z, et al. Mechanism of interactions between CMC binder and Si single crystal facets[J]. Langmuir, 2014, 30(34):10299-10307.
[40] KLAMOR S, SCHRODER M, BRUNKLAUS G, et al. On the interaction of water-soluble binders and nano silicon particles:Alternative binder towards increased cycling stability at elevated temperatures[J]. Phys. Chem. Chem. Phys., 2015, 17(8):5632-5641.
[41] COURTEL F M, NIKETIC S, DUGUAY D, et al. Water-soluble binders for MCMB carbon anodes for lithium-ion batteries[J]. J. Power Sources, 2011, 196(4):2128-2134.
[42] HUANG H J, HAN G S, XIE J Y, et al. The effect of commercialized binders on silicon oxide anode material for high capacity lithium ion batteries[J]. Int. J. Electrochem. Sci., 2016, 11(10):8697-8708.
[43] YUE L, ZHANG L Z, ZHONG H X. Carboxymethyl chitosan:A new water soluble binder for Si anode of Li-ion batteries[J]. J. Power Sources, 2014, 247(1):327-331.
[44] QIU L W, SHEN Y D, FAN H B, et al. Carboxymethyl fenugreek gum:Rheological characterization and as a novel binder for silicon anode of lithium-ion batteries[J]. Int. J. Biol. Macromol., 2018, 115(1):672-679.
[45] LU L, LOU H M, XIAO Y L, et al. Synthesis of triblock copolymer polydopamine-polyacrylic-polyoxyethylene with excellent performance as a binder for silicon anode lithium-ion batteries[J]. RSC Adv., 2018, 8(9):4604-4609.
[46] MARKEVICH E, SHARABI R, BORGEL V, et al. In situ FTIR study of the decomposition of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) amide ionic liquid during cathodic polarization of lithium and graphite electrodes[J]. Electrochim. Acta, 2010, 55(8):2687-2696.
[47] JOHO F, NOVAK P. SNIFTIRS investigation of the oxidative decomposition of organic-carbonate-based electrolytes for lithium-ion cells[J]. Electrochim. Acta, 2000, 45(21):3589-3599.
[48] MOSHKOVICH M, COJOCARU M, GOTTLIEB H E, et al. The study of the anodic stability of alkyl carbonate solutions by in situ FTIR spectroscopy, EQCM, NMR and MS[J]. J. Electrochem. Chem., 2001, 497(2):84-96.
[49] ZHU Z Q, CHENG F Y, CHEN J. Investigation of effects of carbon coating on the electrochemical performance of Li₄Ti₅O₁₂/C nanocomposites[J]. J. Mater. Chem. A, 2013, 1(33):9484-9490.
[50] GROSS T, GIEBELER L, HESS C. Novel in situ cell for Raman diagnostics of lithium-ion batteries[J]. Rev. Sci. Instrum., 2013, 84(7):doi:10.1063/1.4813263.
[51] HOLZAPFEL M, BUQA H, HARDWICK L J, et al. Nano silicon for lithium-ion batteries[J]. Electrochim. Acta, 2006, 52(3):973-978.
[52] PENG Z Q, FREUNBERGER S A, HARDWICK L J, et al. Oxygen reactions in a non-aqueous Li⁺ electrolyte[J]. Angew. Chem. Int. Ed., 2011, 50(28):6351-6355.
[53] CHEN J J, YUAN R M, FENG J M, et al. Conductive lewis base matrix to recover the missing link of Li₂S₈ during the sulfur redox cycle in Li-S battery[J]. Chem. Mater., 2015, 27(6):2048-2055.
[54] XIANG H F, WANG H, CHEN C H, et al. Thermal stability of LiPF₆-based electrolyte and effect of contact with various delithiated cathodes of Li-ion batteries[J]. J. Power Sources, 2009, 191(2):575-581.
[55] BADDOUR-HADJEAN R, NAVONE C, PEREIRA-RAMOS J P. In situ Raman microspectrometry investigation of electrochemical lithium intercalation into sputtered crystalline V₂O₅ thin films[J]. Electrochim. Acta, 2009, 54(26):6674-6679.
[56] CHENG Q, WEI L, LIU Z, et al. Operando and three-dimensional visualization of anion depletion and lithium growth by stimulated Raman scattering microscopy[J]. Nat. Commun., 2018, 9:doi:10.1038/s41467-018-05289-z.
[57] MATSUO Y, KOSTECKI R, MCLARNON F. Surface layer formation on thin-film LiMn₂O₄ electrodes at elevated temperatures[J]. J. Electrochem. Soc., 2001, 148(7):A687-A692.
[58] GITTLESON F S, RYU W H, TAYLOR A D. Operando observation of the gold-electrolyte interface in Li-O₂ batteries[J]. ACS Appl. Mater. Interfaces, 2014, 6(21):19017-19025.
[59] ZHAO Z W, SU Y W, PENG Z Q. Probing lithium carbonate formation in trace o-assisted aprotic Li-CO₂ batteries using in-situ surface enhanced Raman spectroscopy[J]. J. Phys. Chem. Lett., 2019, 10(3):322-328.
[60] HY S, FELIX F, RICK J, et al. Direct in situ observation of Li₂O evolution on Li-rich high-capacity cathode material, Li[Ni_xLi_(1-2x)/3Mn_(2-x)/3] O₂ (0≤ x ≤ 0.5)[J]. J. Am. Chem. Soc., 2014, 136(3):999-1007.
[61] ZENG Z C, HUANG S C, WU D Y, et al. Electrochemical tipenhanced Raman spectroscopy[J]. J. Am. Chem. Soc., 2015, 137(37):11928-11931.
[62] DHAND V, RAO V M, MITTAL G, et al. Synthesis of lithiumgraphite nanotubes-An in-situ CVD approach using organo-lithium as a precursor in the presence of copper[J]. Current Applied Physics, 2015, 15(3):265-273.
[63] WANG X, XING W Y, FENG X M, et al. The effect of metal oxide decorated graphene hybrids on the improved thermal stability and the reduced smoke toxicity in epoxy resins[J]. Chem. Eng. J., 2014, 250(1):214-221.
[64] WANG Z X, HUANG X J, CHEN L Q. Characterization of spontaneous reactions of LiCoO₂ with electrolyte solvent for lithiumion batteries[J]. J. Electrochem. Soc., 2004, 151(10):A1641-A1652.
[65] OTOYAMA M, ITO Y, HAYASHI A, et al. Investigation of state-ofcharge distributions for LiCoO₂ composite positive electrodes in allsolid-state lithium batteries by Raman imaging[J]. Chem. Lett., 2016, 45(7):810-812.
[66] SAQIB N, SILVA C J, MAUPIN C M, et al. A novel optical diagnostic for in situ measurements of lithium polysulfides in battery electrolytes[J]. Appl. Spectrosc., 2017, 71(7):1593-1599.
[67] ITOH T, SATO H, NISHINA T, et al. In situ Raman spectroscopic study of LixCoO₂ electrodes in propylene carbonate solvent systems[J]. J. Power Sources, 1997, 68(2):333-337.
[68] JULIEN C M, MASSOT M. Lattice vibrations of materials for lithium rechargeable batteries I. Lithium manganese oxide spinel[J]. Mater. Sci. Eng. B, 2003, 97(3):217-230.
[69] BURBA C M, FRECH R. Raman and FTIR spectroscopic study of Li_xFePO₄ (0≤ x ≤ 1)[J]. J. Electrochem. Soc., 2004, 151(7):A1032-A1038.
[70] BADDOUR-HADJEAN R, PEREIRA-RAMOS J P. Raman microspectrometry applied to the study of electrode materials for lithium batteries[J]. Chem. Rev., 2010, 110(3):1278-1319.
[71] TUINSTRA F, KOENIG J L. Raman spectrum of graphite[J]. J. Chem. Phys., 1970, 53(3):1126-1130.
[72] WANG Q, LI H, CHEN L Q, et al. Novel spherical microporous carbon as anode material for Li-ion batteries[J]. Solid State Ionics, 2002, 152(SI):43-50.
[73] IQBAL Z, VEPREK S. Raman-scattering from hydrogenated microcrystalline and amorphous silicon[J]. J. Phy. C, 1982, 15(2):377-392.
[74] JULIEN C M, MASSOT M, ZAGHIB K. Structural studies of Li_4/3Me_5/3O₄ (Me=Ti, Mn) electrode materials:Local structure and electrochemical aspects[J]. J. Power Sources, 2004, 136(1):72-79.
[75] BADDOUR-HADJEAN R, BACH S, SMIRNOV M, et al. Raman investigation of the structural changes in anatase Li_xTiO₂ upon electrochemical lithium insertion[J]. J. Raman Spectrosc., 2004, 35(7):577-585.
[76] BADDOUR-HADJEAN R, PEREIRA-RAMOS J P, NAVONE C, et al. Raman microspectrometry study of electrochemical lithium intercalation into sputtered crystalline V₂O₅ thin films[J]. Chem. Mater., 2008, 20(5):1916-1923.
[77] RISTIC M, IVANDA M, POPOVIC S, et al., Dependence of nanocrystalline SnO₂ particle size on synthesis route[J]. J. Non-Cryst. Solids, 2002, 303(2):270-280.
[78] IKEZAWA Y, ARIGA T. In situ FTIR spectra at the Cu electrode/propylene carbonate solution interface[J]. Electrochim. Acta, 2007, 52(7):2710-2715.
[79] JOHO F, NOVÁK P. SNIFTIRS investigation of the oxidative decomposition of organic-carbonate-based electrolytes for lithium-ion cells[J]. Electrochim. Acta, 2000, 45(21):3589-3599.