Abstract
Owing to the high spatial resolution at the atomic scale, the transmission electron microscopy (TEM) or scanning transmission electron microscopy is demonstrated as a promising characterization method to unveil the charge storage mechanism of electrode materials in Li-ion batteries. The structural evolution of electrode materials during charge/discharge process can be directly observed by using TEM. The detailed analysis establishes a relationship between the structure of electrode material and battery performance. Herein, we present a brief review of the atomic-scale characterization in Li-ion batteries, including Li (de)insertion mechanism (both cations and anions charge-compensation mechanism), migration of transition metal ions, and surface phase transition. The in-depth microscopic analysis reveals the detailed structural characteristics, which influence the properties of LIBs, establish the structure–function relationship, and facilitate the development of Li-ion batteries.
Similar content being viewed by others
References
Armand M, Tarascon JM. Building better batteries. Nature. 2008;451(7179):652.
Pennycook SJ, Boatner LA. Chemically sensitive structure-imaging with a scanning-transmission electron-microscope. Nature. 1988;336(6199):565.
Findlay SD, Shibata N, Sawada H, Okunishi E, Kondo Y, Ikuhara Y. Dynamics of annular bright field imaging in scanning transmission electron microscopy. Ultramicroscopy. 2010;110(7):903.
Oshima Y, Sawada H, Hosokawa F, Okunishi E, Kaneyama T, Kondo Y, Niitaka S, Takagi H, Tanishiro Y, Takayanagi K. Direct imaging of lithium atoms in LiV2O4 by spherical aberration-corrected electron microscopy. J Electron Microsc (Tokyo). 2010;59(6):457.
Lu X, Jian Z, Fang Z, Gu L, Hu Y-S, Chen W, Wang Z, Chen L. Atomic-scale investigation on lithium storage mechanism in TiNb2O7. Energy Environ Sci. 2011;4(8):2638.
Lee J, Zhou W, Idrobo JC, Pennycook SJ, Pantelides ST. Vacancy-driven anisotropic defect distribution in the battery-cathode material LiFePO4. Phys Rev Lett. 2011;107(8):5507.
Huang R, Ikuhara YH, Mizoguchi T, Findlay SD, Kuwabara A, Fisher CA, Moriwake H, Oki H, Hirayama T, Ikuhara Y. Oxygen-vacancy ordering at surfaces of lithium manganese(III, IV) oxide spinel nanoparticles. Angew Chem Int Ed Engl. 2011;50(13):3053.
Huang R, Hitosugi T, Findlay SD, Fisher CAJ, Ikuhara YH, Moriwake H, Oki H, Ikuhara Y. Real-time direct observation of Li in LiCoO2 cathode material. Appl Phys Lett. 2011;98(5):051913.
Gao X, Fisher CAJ, Kimura T, Ikuhara YH, Moriwake H, Kuwabara A, Oki H, Tojigamori T, Huang R, Ikuhara Y. Lithium atom and A-site vacancy distributions in lanthanum lithium titanate. Chem Mater. 2013;25(9):1607.
Gu L, Zhu C, Li H, Yu Y, Li C, Tsukimoto S, Maier J, Ikuhara Y. Direct observation of lithium staging in partially delithiated LiFePO4 at atomic resolution. J Am Chem Soc. 2011;133(13):4661.
Suo L, Han W, Lu X, Gu L, Hu YS, Li H, Chen D, Chen L, Tsukimoto S, Ikuhara Y. Highly ordered staging structural interface between LiFePO4 and FePO4. Phys Chem Chem Phys. 2012;14(16):5363.
Sun Y, Lu X, Xiao R, Li H, Huang X. Kinetically controlled lithium-staging in delithiated LiFePO4. Driven by the Fe center mediated interlayer Li–Li interactions. Chem Mater. 2012;24(24):4693.
Zhu C, Gu L, Suo L, Popovic J, Li H, Ikuhara Y, Maier J. Size-dependent staging and phase transition in LiFePO4/FePO4. Adv Func Mater. 2014;24(3):312.
Niu J, Kushima A, Qian X, Qi L, Xiang K, Chiang Y-M, Li J. In situ observation of random solid solution zone in LiFePO4 electrode. Nano Lett. 2014;14(7):4005.
Zhu Y, Wang JW, Liu Y, Liu X, Kushima A, Liu Y, Xu Y, Mao SX, Li J, Wang C, Huang JY. In situ atomic-scale imaging of phase boundary migration in FePO4 microparticles during electrochemical lithiation. Adv Mater. 2013;25(38):5461.
Liu XH, Zheng H, Zhong L, Huang S, Karki K, Zhang LQ, Liu Y, Kushima A, Liang WT, Wang JW, Cho JH, Epstein E, Dayeh SA, Picraux ST, Zhu T, Li J, Sullivan JP, Cumings J, Wang C, Mao SX, Ye ZZ, Zhang S, Huang JY. Anisotropic swelling and fracture of silicon nanowires during lithiation. Nano Lett. 2011;11(8):3312.
He K, Zhang S, Li J, Yu X, Meng Q, Zhu Y, Hu E, Sun K, Yun H, Yang XQ, Zhu Y, Gan H, Mo Y, Stach EA, Murray CB, Su D. Visualizing non-equilibrium lithiation of spinel oxide via in situ transmission electron microscopy. Nat Commun. 2016;7:11441.
Wang F, Yu HC, Chen MH, Wu L, Pereira N, Thornton K, Van der Ven A, Zhu Y, Amatucci GG, Graetz J. Tracking lithium transport and electrochemical reactions in nanoparticles. Nat Commun. 2012;3:1201.
Gong Y, Chen Y, Zhang Q, Meng F, Shi JA, Liu X, Liu X, Zhang J, Wang H, Wang J, Yu Q, Zhang Z, Xu Q, Xiao R, Hu YS, Gu L, Li H, Huang X, Chen L. Three-dimensional atomic-scale observation of structural evolution of cathode material in a working all-solid-state battery. Nat Commun. 2018;9:3341.
Gong Y, Zhang J, Jiang L, Shi JA, Zhang Q, Yang Z, Zou D, Wang J, Yu X, Xiao R, Hu YS, Gu L, Li H, Chen L. In situ atomic-scale observation of electrochemical delithiation induced structure evolution of LiCoO2 cathode in a working all-solid-state battery. J Am Chem Soc. 2017;139(12):4274.
Lu J, Wu T, Amine K. State-of-the-art characterization techniques for advanced lithium-ion batteries. Nat Energy. 2017;2(3):17011.
Lu X, Zhao L, He X, Xiao R, Gu L, Hu YS, Li H, Wang Z, Duan X, Chen L, Maier J, Ikuhara Y. Lithium storage in Li4Ti5O12 spinel: the full static picture from electron microscopy. Adv Mater. 2012;24(24):3233.
Ohzuku T, Ueda A, Yamamoto N. Zero-strain insertion material of Li[Li1/3Ti5/3]O4 for rechargeable lithium cells. J Electrochem Soc. 1995;142(5):1431.
Ferg E, Gummow RJ, Dekock A, Thackeray MM. Spinel anodes for lithium anodes for lithium-ion batteries. J Electrochem Soc. 1994;141(11):L147.
Slater MD, Kim D, Lee E, Johnson CS. Sodium-ion batteries. Adv Func Mater. 2013;23(8):947.
Pan H, Hu YS, Chen L. Room-temperature stationary sodium-ion batteries for large-scale electric energy storage. Energy Environ Sci. 2013;6(8):2338.
Zhao L, Pan HL, Hu YS, Li H, Chen LQ. Spinel lithium titanate (Li4Ti5O12) as novel anode material for room-temperature sodium-ion battery. Chin Phys B. 2012;21(2):8201.
Sun Y, Zhao L, Pan H, Lu X, Gu L, Hu YS, Li H, Armand M, Ikuhara Y, Chen L, Huang X. Direct atomic-scale confirmation of three-phase storage mechanism in Li4Ti5O12 anodes for room-temperature sodium-ion batteries. Nat Commun. 2013;4:1870.
Sathiya M, Ramesha K, Rousse G, Foix D, Gonbeau D, Prakash AS, Doublet ML, Hemalatha K, Tarascon JM. High performance Li2Ru1−yMnyO3 (0.2 ≤ y ≤ 0.8) cathode materials for rechargeable lithium-ion batteries: their understanding. Chem Mater. 2013;25(7):1121.
Sathiya M, Rousse G, Ramesha K, Laisa CP, Vezin H, Sougrati MT, Doublet ML, Foix D, Gonbeau D, Walker W, Prakash AS, Ben Hassine M, Dupont L, Tarascon JM. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nat Mater. 2013;12(9):827.
Sathiya M, Abakumov AM, Foix D, Rousse G, Ramesha K, Saubanere M, Doublet ML, Vezin H, Laisa CP, Prakash AS, Gonbeau D, VanTendeloo G, Tarascon JM. Origin of voltage decay in high-capacity layered oxide electrodes. Nat Mater. 2015;14(2):230.
McCalla E, Abakumov AM, Saubanere M, Foix D, Berg EJ, Rousse G, Doublet ML, Gonbeau D, Novak P, Van Tendeloo G, Dominko R, Tarascon JM. Visualization of O–O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries. Science. 2015;350(6267):1516.
Lee J, Urban A, Li X, Su D, Hautier G, Ceder G. Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries. Science. 2014;343(6170):519.
Zhao E, He L, Wang B, Li X, Zhang J, Wu Y, Chen J, Zhang S, Liang T, Chen Y, Yu X, Li H, Chen L, Huang X, Chen H, Wang F. Structural and mechanistic revelations on high capacity cation-disordered Li-rich oxides for rechargeable Li-ion batteries. Energy Storage Mater. 2019;16:354.
Liu X, Gu L. Advanced transmission electron microscopy for electrode and solid-electrolyte materials in lithium-ion batteries. Small Methods. 2018;2(8):1800006.
Wen Y, Shang T, Gu L. Analytical ABF-STEM imaging of Li ions in rechargeable batteries. Microscopy. 2017;66(1):25.
Oshima Y, Lee S, Takayanagi K. Visualization of lithium ions by annular bright field imaging. Microscopy. 2017;66(1):15.
Findlay SD, Huang R, Ishikawa R, Shibata N, Ikuhara Y. Direct visualization of lithium via annular bright field scanning transmission electron microscopy: a review. Microscopy. 2017;66(1):3.
Gu L, Xiao D, Hu YS, Li H, Ikuhara Y. Atomic-scale structure evolution in a quasi-equilibrated electrochemical process of electrode materials for rechargeable batteries. Adv Mater. 2015;27(13):2134.
Xiao D, Gu L. Atomic-scale structure of nearly-equilibrated electrode materials under lithiation/delithiation for lithium-ion batteries. Scientia Sinica Chimica. 2014;44(3):295.
Wang R, He X, He L, Wang F, Xiao R, Gu L, Li H, Chen L. Atomic structure of Li2MnO3 after partial delithiation and re-lithiation. Adv Energy Mater. 2013;3(10):1358.
Yu DYW, Yanagida K. Structural analysis of Li2MnO3 and related Li–Mn–O materials. J Electrochem Soc. 2011;158(9):A1015.
Susai FA, Sclar H, Shilina Y, Penki TR, Raman R, Maddukuri S, Maiti S, Halalay IC, Luski S, Markovsky B, Aurbach D. Horizons for Li-ion batteries relevant to electro-mobility: high-specific-energy cathodes and chemically active separators. Adv Mater. 2018;30(41):1801348.
Liang C, Kong F, Longo RC, Kc S, Kim JS, Jeon S, Choi S, Cho K. Unraveling the origin of instability in Ni-rich LiNi1−2xCoxMnxO2 (NCM) cathode materials. J Phys Chem C. 2016;120(12):6383.
Yan P, Zheng J, Zhang JG, Wang C. Atomic resolution structural and chemical imaging revealing the sequential migration of Ni Co, and Mn upon the battery cycling of layered cathode. Nano Lett. 2017;17(6):3946.
Lin Q, Guan W, Meng J, Huang W, Wei X, Zeng Y, Li J, Zhang Z. A new insight into continuous performance decay mechanism of Ni-rich layered oxide cathode for high energy lithium ion batteries. Nano Energy. 2018;54:313.
Lu X, Sun Y, Jian Z, He X, Gu L, Hu YS, Li H, Wang Z, Chen W, Duan X, Chen L, Maier J, Tsukimoto S, Ikuhara Y. New insight into the atomic structure of electrochemically delithiated O3–Li(1–x)CoO2 (0 ≤ x ≤ 0.5) nanoparticles. Nano Lett. 2012;12(12):6192.
Lin F, Markus IM, Nordlund D, Weng T-C, Asta MD, Xin HL, Doeff MM. Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries. Nat Commun. 2014;5:3529.
Zheng H, Sun Q, Liu G, Song X, Battaglia VS. Correlation between dissolution behavior and electrochemical cycling performance for LiNi1/3Co1/3Mn1/3O2-based cells. J Power Sour. 2012;207:134.
Ryu HH, Park KJ, Yoon CS, Sun YK. Capacity fading of Ni-rich Li[NixCoyMn1–x–y]O2 (0.6 ≤ x ≤ 0.95) cathodes for high-energy-density lithium-ion batteries: bulk or surface degradation? Chem Mater. 2018;30(3):1155.
Schipper F, Dixit M, Kovacheva D, Talianker M, Haik O, Grinblat J, Erickson EM, Ghanty C, Major DT, Markovsky B, Aurbach D. Stabilizing nickel-rich layered cathode materials by a high-charge cation doping strategy: zirconium-doped LiNi0.6Co0.2Mn0.2O2. J Mater Chem A. 2016;4(41):16073.
Chen JS, Wang LF, Fang BJ, Lee SY, Guo RZ. Rotating ring-disk electrode measurements on Mn dissolution and capacity losses of spinel electrodes in various organic electrolytes. J Power Sour. 2006;157(1):515.
Wang LF, Ou CC, Striebel KA, Chen JJS. Study of mn dissolution from LiMn2O4 spinel electrodes using rotating ring-disk collection experiments. J Electrochem Soc. 2003;150(7):A905.
Tang D, Sun Y, Yang Z, Ben L, Gu L, Huang X. Surface structure evolution of LiMn2O4 cathode material upon charge/discharge. Chem Mater. 2014;26(11):3535.
Tang D, Ben L, Sun Y, Chen B, Yang Z, Gu L, Huang X. Electrochemical behavior and surface structural change of LiMn2O4 charged to 5.1 V. J Mater Chem A. 2014;2(35):14519.
Ben LB, Yu HL, Chen B, Chen YY, Gong Y, Yang XA, Gu L, Huang XJ. Unusual spinel-to-layered transformation in LiMn2O4 cathode explained by electrochemical and thermal stability investigation. ACS Appl Mater Int. 2017;9(40):35463.
Hu LH, Wu FY, Lin CT, Khlobystov AN, Li LJ. Graphene-modified LiFePO4 cathode for lithium ion battery beyond theoretical capacity. Nat Commun. 2013;4:1687.
Jung SK, Kim H, Cho MG, Cho SP, Lee B, Kim H, Park YU, Hong J, Park KY, Yoon G, Seong WM, Cho Y, Oh MH, Kim H, Gwon H, Hwang I, Hyeon T, Yoon WS, Kang K. Lithium-free transition metal monoxides for positive electrodes in lithium-ion batteries. Nat Energy. 2017;2(2):16208.
Lozano JG, Martinez GT, Jin L, Nellist PD, Bruce PG. Low-dose aberration-free imaging of Li-rich cathode materials at various states of charge using electron ptychography. Nano Lett. 2018;18(11):6850.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (Nos. 51672307 and 51421002), the Strategic Priority Research Program of Chinese Academy of Sciences (CAS) (No. XDB07030200) and the Key Research Program of Frontier Sciences, CAS (No. QYZDB-SSW-JSC035).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Ji, YR., Weng, ST., Li, XY. et al. Atomic-scale structural evolution of electrode materials in Li-ion batteries: a review. Rare Met. 39, 205–217 (2020). https://doi.org/10.1007/s12598-020-01369-6
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12598-020-01369-6