拉曼光谱在锂离子电池研究中的应用

doi:10.61558/2993-074X.2814

摘要/Abstract

摘要： 综述拉曼光谱(Raman spectroscopy)在锂离子电池碳负极材料、尖晶石LiMn2O4和LiFePO4正极材料、聚合物和室温熔盐电解质以及电极/电解质界面膜研究中的应用,分析了非原位拉曼测试手段与原位拉曼测试手段的优缺点,展望了这一领域目前有待解决的问题和可能应用的新技术.

关键词: 拉曼光谱, 锂离子电池, 负极材料, 正极材料, 聚合物电解质, 室温熔盐电解质, 电极-电解质界面, 表面增强拉曼散射(SERS)

Abstract: The Raman spectroscopy has been widely used in the study of lithium ion batteries.In this short review,we gave some examples of the applications of Raman spectroscopy in the study of electrode materials including carbonaceous materials,spinel LiMxMn2-x O4,LiFePO4,as well as polymer electrolytes,room temperaturemolten salt electrolytes and the solid-electrolyte interphase layers.The advantages and disadvantages of the ex-situ and in-situ Raman spectrum techniques are discussed.Using new Raman techniques to investigate Li-ion batteries are suggested.

Key words: Raman spectroscopy, lithium ion batteries, anode materials, cathode materials, polymer electrolytes, room temperature molten salt electrolytes, solid-electrolyte interphase(SEI), surface enhanced Ramanscattering(SERS)

中图分类号:

TM912

赵亮, 胡勇胜, 李泓, 王兆翔, 徐红星, 黄学杰, 陈立泉. 拉曼光谱在锂离子电池研究中的应用[J]. 电化学（中英文）, 2011, 17(1): 12-23.

ZHAO Liang, HU Yong-Sheng, LI Hong, WANG Zhao-Xiang, XU Hong-Xing, HUANG Xue-Jie, CHEN Li-Quan. Applications of Raman Spectroscopy Technique in Lithium Ion Batteries[J]. Journal of Electrochemistry, 2011, 17(1): 12-23.

参考文献

[1]Baddour-Hadjean R,Pereira-Ramos J P.Raman mi-crospectrometry applied to the study of electrode mate-rials for lithium batteries[J].Chem Rev,2010,110(3):1278-1319.

[2]Tuinstra F,Koenig J L.Raman spectrum of graphite[J].J Chem Phys,1970,53(3):1126.

[3]Mabuchi A,Tokumitsu K,Fujimoto H,et al.Charge-discharge characteristics of the mesocarbon microbeadsheat-treated at different temperatures[J].J Electro-chem Soc,1995,142(4):1041-1046.

[4]Inaba M,Yoshida H,Ogumi Z.In-situ Raman study ofelectrochemical lithium insertion into mesocarbon mi-crobeads heat-treated at various temperature[J].JElectrochem Soc,1996,143(8):2572-2578.

[5]Julien C M,Massot M.Lattice vibrations of materialsfor lithium rechargeable batteries I.Lithium manga-nese oxide spinel[J].Mater Sci Eng B,2003,97(3):217-230.

[6]Hwang S J,Park D H,Choy J H,et al.Effect of chromi-um substitution on the lattice vibration of spinel lithiummanganate:A new interpretation of the Raman spec-trum of LiMn2O4[J].J Phys Chem B,2004,108(34):12713-12717.

[7]Li G H,Ikuta H,Uchida T,et al.The spinel phasesLiM(y)Mn(2-y)O(4)(M=Co,Cr,Ni)as the cathode forrechargeable lithium batteries[J].J Electrochem Soc,1996,143(1):178-182.

[8]Song D,Ikuta H,Uchida T,et al.The spinel phases Li-AlyMn2-yO4(y=0,1/12,1/9,1/6,1/3)and Li(Al,M)(1/6)Mn11/6 O4(M=Cr,Co)as the cathode for re-chargeable lithium batteries[J].Solid State Ionics,1999,117(1/2):151-156.

[9]Wei Y J,Kim K B,Chen G.Evolution of the local struc-ture and electrochemical properties of spinel LiNixMn2-x-O4(0<=x<=0.5)[J].Electrochim Acta,2006,51(16):3365-3373.

[10]Amdouni N,Zaghib K,Gendron F,et al.Magneticproperties of LiNi0.5 Mn1.5 O4 spinels prepared by wetchemical methods[J].J Magn Magn Mater,2007,309(1):100-105.

[11]Itoh T,Sato H,Nishina T,et al.In situ Raman spec-troscopic study of LixCoO2 electrodes in propylenecarbonate solvent systems[J].J Power Sources,1997,68(2):333-337.

[12]Iqbal Z,Veprek S.Raman-scattering from hydrogena-ted microcrystalline and amorphous silicon[J].J PhysC,1982,15(2):377-392.

[13]Julien C M,Massot M,Zaghib K.Structural studies ofLi4/3Me5/3O4(Me=Ti,Mn)electrode materials:localstructure and electrochemical aspects[J].J PowerSources,2004,136(1):72-79.

[14]Baddour-Hadjean R,Bach S,Smirnov M,et al.Ramaninvestigation of the structural changes in anataseLixTiO2 upon electrochemical lithium insertion[J].JRaman Spectrosc,2004,35(7):577-585.

[15]Baddour-Hadjean R,Pereira-Ramos J P,Navone C,etal.Raman microspectrometry study of electrochemicallithium intercalation into sputtered crystalline V2O5thin films[J].Chem Mater,2008,20(5):1916-1923.

[16]Wang Z X,Huang B Y,Xue R J,et al.Ion associationand solvation studies of LiClO4 ethylene carbonate e-lectrolyte by Raman and infrared spectroscopy[J].JElectrochem Soc,1998,145(10):3346-3350.

[17]Wang Z X,Huang B Y,Huang H,et al.A vibrationalspectroscopic study on the interaction between lithiumsalt and ethylene carbonate plasticizer for PAN-basedelectrolytes[J].J Electrochem Soc,1996,143(5):1510-1514.

[18]Wang Z X,Huang B Y,Huang H,et al.Investigationof the position of Li ions in a polyacrylonitrile-basedelectrolyte by Raman and infrared spectroscopy[J].Electrochim Acta,1996,41(9):1443-1446.

[19]Wang Z X,Huang B Y,Wang S M,et al.Competitionbetween the plasticizer and polymer on associatingwith Li ions in polyacrylonitrile-based electrolytes[J].J Electrochem Soc,1997,144(3):778-786.

[20]Wang Z X,Huang B Y,Wang S M,et al.Vibrationalspectroscopic investigation of polyacrylonitrile-basedelectrolytes with a dimethylformamide plasticizer[J].J Electrochem Soc,1997,144(1):44-48.

[21]Wang Z X,Huang B Y,Huang H,et al.Experimentalevidence of the interaction between polyacrylonitrileand ethylene carbonate plasticizer by Raman spectros-copy[J].J Raman Spectrosc,1996,27(8):609-613.

[22]Hu Y S,Li H,Huang X J,et al.Novel room tempera-ture molten salt electrolyte based on LiTFSI and ac-etamide for lithium batteries[J].Electrochem Com-mun,2004,6(1):28-32.

[23]Hu Y S,Wang Z X,Li H,et al.Spectroscopic studieson the mechanism of liquid formation and ionic con-ductivity in the LiCF3SO3/acetamide complex system[J].Vib Spectrosc,2005,37(1):1-10.

[24]Hu Y S,Wang Z X,Li H,et al.Spectroscopic studieson the cation-anion,cation-solvent and anion-solventinteractions in the LiCF3SO3/acetamide complex sys-tem[J].Spectrochim Acta Part A,2005,61(3):403-411.

[25]Wang Q,Li H,Chen L Q,et al.Monodispersed hardcarbon spherules with uniform nanopores[J].Carbon,2001,39(14):2211-2214.

[26]Wang Q,Li H,Chen L Q,et al.Novel spherical micro-porous carbon as anode material for Li-ion batteries[J].Solid State Ionics,2002,152(SI):43-50.

[27]Hu J,Li H,Huang X J.Electrochemical behavior andmicrostructure variation of hard carbon nano-spherulesas anode material for Li-ion batteries[J].Solid StateIonics,2007,178(3/4):265-271.

[28]Gibot P,Casas-Cabanas M,Laffont L,et al.Room-tem-perature single-phase Li insertion/extraction innanoscale LixFePO4[J].Nature Mater,2008,7(9):741-747.

[29]Paquesle M,Tarte P.Vibrational Studies of olivine-type compounds 2.orthophosphates,orthoarsenatesand orthovanadates AIBIIXVO4[J].Spectrochim ActaPart A,1974,A30(3):673-689.

[30]Burba C M,Frech R.Raman and FTIR spectroscopicstudy of LixFePO4(0<=x<=1)[J].J ElectrochemSoc,2004,151(7):A1032-A1038.

[31]Aurbach D.The electrochemical-behavior of lithiumsalt-solutions of gamma-butyrolactone with noble-met-al electrodes[J].J Electrochem Soc,1989,136(4):906-913.

[32]Aurbach D,Markovsky B,Weissman I,et al.On thecorrelation between surface chemistry and performanceof graphite negative electrodes for Li ion batteries[J].Electrochim Acta,1999,45(1/2):67-86.

[33]Aurbach D,Gamolsky K,Markovsky B,et al.The stud-y of surface phenomena related to electrochemicallithium intercalation into LixMOy host materials(M=Ni,Mn)[J].J Electrochem Soc,2000,147(4):1322-1331.

[34]Li H,Huang X J,Chen L Q.Direct imaging of the pas-sivating film and microstructure of nanometer-scaleSnO anodes in lithium rechargeable batteries[J].Electrochem Solid State Lett,1998,1(6):241-243.

[35]Kneipp K,Wang Y,Kneipp H,et al.Single moleculedetection using surface-enhanced Raman scattering(SERS)[J].Phys Rev Lett,1997,78(9):1667-1670.

[36]Tian Z Q,Ren B,Wu D Y.Surface-enhanced Ramanscattering:From noble to transition metals and fromrough surfaces to ordered nanostructures[J].J PhysChem B,2002,106(37):9463-9483.

[37]Xu H X,Bjerneld E J,Kall M,et al.Spectroscopy ofsingle hemoglobin molecules by surface enhanced Ra-man scattering[J].Phys Rev Lett,1999,83(21):4357-4360.

[38]Li H,Mo Y J,Pei N,et al.Surface-enhanced Ramanscattering study on passivating films of Ag electrodesin lithium batteries[J].J Phys Chem B,2000,104(35):8477-8480.

[39]Li G F,Li H,Mo Y J,et al.Further identification tothe SEI film on Ag electrode in lithium batteries bysurface enhanced Raman scattering(SERS)[J].JPower Sources,2002,104(2):190-194.

[40]Dong B,Huang Y Z,Yu N S,et al.Local and remoteCharge-transfer-enhanced Raman scattering on one-di-mensional transition-metal oxides[J].Chem Asian J,2010,5(8):1824-1829.

[41]Li J F,Huang Y F,Ding Y,et al.Shell-isolated nano-particle-enhanced Raman spectroscopy[J].Nature,2010,464(7287):392-395.

[42]Pettinger B,Ren B,Picardi G,et al.Nanoscale pro-bing of adsorbed species by tip-enhanced Ramanspectroscopy[J].Phys Rev Lett,2004,92(9).

[43]Lei J L,McLarnon F,Kostecki R.In situ Raman mi-croscopy of individual LiNi0.8 Co0.15 Al0.05 O2 particlesin a Li-ion battery composite cathode[J].J PhysChem B,2005,109(2):952-957.

[44]Hardwick L J,Holzapfel M,Novak P,et al.Electro-chemical lithium insertion into anatase-type TiO2:Anin-situ Raman microscopy investigation[J].Electro-chim Acta,2007,52(17):5357-5367.

[45]Huang W W,Frech R.In situ Raman spectroscopicstudies of electrochemical intercalation in LixMn2O4-based cathodes:9th International Meeting on LithiumBatteries,Edinburgh,July12-17,1998[C].Lausanne:Elsevier,c1999.

[46]Zhang X L,Frech R.In situ Raman spectroscopy ofLixV2O5 in a lithium rechargeable battery[J].J Elec-trochem Soc,1998,145(3):847-851.

[47]Baddour-Hadjean R,Navone C,Pereira-Ramos J P.Insitu Raman microspectrometry investigation of electro-chemical lithium intercalation into sputtered crystal-line V2O5 thin films[J].Electrochim Acta,2009,54(26):6674-6679.

[48]Huang W W,Frech P.In situ Raman studies of graph-ite surface structures during lithium electrochemicalintercalation[J].J Electrochem Soc,1998,145(3):765-770.

[49]Panitz J C,Joho F,Novak P.In situ characterization ofa graphite electrode in a secondary lithium-ion batteryusing Raman microscopy[J].Appl Spectrosc,1999,53(10):1188-1199.

[50]Hardwick L J,Buqa H,Holzapfel M,et al.Behaviourof highly crystalline graphitic materials in lithium-ioncells with propylene carbonate containing electrolytes:An in situ Raman and SEM study[J].ElectrochimActa,2007,52(15):4884-4891.

[51]Dokko K,Mohamedi M,Anzue N,et al.In situ Ramanspectroscopic studies of LiNixMn2-x O4 thin film cath-ode materials for lithium ion secondary batteries[J].JMater Chem,2002,12(12):3688-3693.

[52]Dokko K,Anzue N,Mohamedi M,et al.Raman spec-tro-electrochemistry of LiCoxMn2-x O4 thin film elec-trodes for 5 V lithium batteries[J].Electrochem Com-mun,2004,6(4):384-388.

[53]Delichere P,Hugotlegoff A,Yu N.Identification by In-situ Raman-spectroscopy of the films grown during thepolarization of nickel in sulfuric solutions[J].J Elec-trochem Soc,1986,133(10):2106-2107.

[54]Cordoba-Torresi S I,Hugot-Le Goff A,Joiret S.Elec-trochromic behavior of nickel-oxide electrodes 2.I-dentification of the bleached state by Raman-spectros-copy and nuclear-reactions[J].J Electrochem Soc,1991,138(6):1554-1559.

[55]Desilvestro J,Corrigan D A,Weaver M J.Spectroelec-trochemistry of thin nickel-hydroxide films on gold u-sing Surface-Enhanced Raman-Spectroscopy[J].JPhys Chem,1986,90(24):6408-6411.

[56]Desilvestro J,Corrigan D A,Weaver M J.Character-ization of redox states of nickel-hydroxide film elec-trodes by in-situ surface Raman spectroscopy[J].JElectrochem Soc,1988,135(4):885-892.

[57]Kerlau M,Marcinek M,Srinivasan V,et al.Studies oflocal degradation phenomena in composite cathodesfor lithium-ion batteries[J].Electrochim Acta,2007,52(17):5422-5429.