锂离子电池中重要正极材料体系的磁共振研究进展

doi:10.19799/j.cnki.2095-4239.2019.0186

摘要/Abstract

摘要： 锂离子电池得到了快速发展，并改变了我们的生活。锂离子电池正极材料的研究是提高电池性能的关键；而理解正极材料的性能与结构之间的关系、阐释正极材料的电化学反应机理（尤其是性能衰减与失效机理）有助于提高材料的能量密度和功率密度。磁共振技术（含核磁共振和顺磁共振）在过去三十多年的研究中不断进步，逐渐成为研究正极材料构效关系的关键技术之一。本文总结了几个重要的已经商业化的正极材料（LiCoO₂、NCA、NMC和LiFePO₄）的磁共振研究进展，展示了核磁共振、顺磁共振在正极材料构效关系研究中的重要作用；尤其值得一提的是原位技术的发展在电化学反应机理中逐渐显示出其重要性。本文有助于了解磁共振技术在电池材料研究中的重要价值，并进一步推动磁共振技术的发展。

关键词: 正极材料, 核磁共振, 顺磁共振

Abstract: Lithium-ion batteries have grown rapidly and have changed our lives. The research on the cathode materials of lithium ion battery is the key to improve the performance of the battery. Therefore, understanding the relationship between the structure-performance relationship and explaining the electrochemical reaction mechanism (especially the performance degradation and failure mechanism) of the cathode materials can help to improve the energy density and power density of the materials. Magnetic Resonance techniques, including NMR (nuclear magnetic resonance) and EPR (electron paramagnetic resonance), has been continuously improved during the past three decades of material research, and has gradually become one of the key technologies for studying the structure-performance relationship of cathode materials. NMR could be used to study light elements commonly found in battery materials such as Li, Na, F, P, C, H and O, while EPR can be employed to study transition metals such as Co, Ni, Mn, Fe and V. This paper summarizes the progress of magnetic resonance research on several important commercial cathode materials (LiCoO₂, NCA, NMC and LiFePO₄), and demonstrates the important role of NMR and EPR in the study of structureperformance relationship of cathode materials. It is emphasized here that the development of in-situ technology has gradually shown its importance to investigate the electrochemical reaction mechanism. This article will help to understand the important value of magnetic resonance technology in battery materials research and further promote the development of magnetic resonance technology.

Key words: cathode material, NMR, EPR

中图分类号:

O641

耿福山, 胡炳文. 锂离子电池中重要正极材料体系的磁共振研究进展[J]. 储能科学与技术, 2019, 8(6): 1017-1023.

GENG Fushan, HU Bingwen. Progress in magnetic resonance research of important cathode materials in lithium ion batteries[J]. Energy Storage Science and Technology, 2019, 8(6): 1017-1023.

参考文献

[1] LARCHER D, TARASCON J M. Towards greener and more sustainable batteries for electrical energy storage[J]. Nature Chemistry, 2014, 7:19.
[2] NITTA N, WU F, LEE J T, et al. Li-ion battery materials:present and future[J]. Materials Today, 2015, 18(5):252-264.
[3] WHITTINGHAM M S. Lithium batteries and cathode materials[J]. Chemical Reviews, 2004, 104(10):4271-4302.
[4] GOODENOUGH J B, PARK K-S. The Li-ion rechargeable battery:A perspective[J]. Journal of the American Chemical Society, 2013, 135(4):1167-1176.
[5] HARKS P P R M L, MULDER F M, NOTTEN P H L. In situ methods for Li-ion battery research:A review of recent developments[J]. Journal of Power Sources, 2015, 288:92-105.
[6] BAK S M, SHADIKE Z, LIN R, et al. In situ/operando synchrotronbased X-ray techniques for lithium-ion battery research[J]. NPG Asia Materials, 2018, 10(7):563-580.
[7] 李超, 沈明, 胡炳文. 面向金属离子电池研究的固体核磁共振和电子顺磁共振方法[J]. 物理化学学报, 2019, 35:0001-0009. LI C, SHEN M, HU B W. Solid-state NMR and EPR methods for metal ion battery research[J]. Acta Physico-Chimica Sinica, 2019, 35:0001-0009.
[8] SIEGEL R, HIRSCHINGER J, CARLIER D, et al. ⁵⁹Co and ^6,7Li MAS NMR in polytypes O₂ and O₃ of LiCoO₂[J]. The Journal of Physical Chemistry B, 2001, 105(19):4166-4174.
[9] MéNéTRIER M, SAADOUNE I, LEVASSEUR S, et al. The insulatormetal transition upon lithium deintercalation from LiCoO₂:Electronic properties and ⁷Li NMR study[J]. Journal of Materials Chemistry, 1999, 9(5):1135-1140.
[10] CAREWSKA M, SCACCIA S, CROCE F, et al. Electrical conductivity and ^6,7Li NMR studies of Li_1+yCoO₂[J]. Solid State Ionics, 1997, 93(3):227-237.
[11] PEETERS M P J, VAN BOMMEL M J, NEILEN-TEN WOLDE P M C, et al. A ⁶Li, ⁷Li and ⁵⁹Co MAS NMR study of rock salt type Li_xCoO₂ (0.48≤ x ≤ 1.05)[J]. Solid State Ionics, 1998, 112(1):41-52.[12 LEVASSEUR S, MéNéTRIER M, SUARD E, et al. Evidence for structural defects in non-stoichiometric HT-LiCoO₂:Electrochemical, electronic properties and ⁷Li NMR studies[J]. Solid State Ionics, 2000, 128(1):11-24.
[13] LEVASSEUR S, MéNéTRIER M, DELMAS C. On the Li_xCo_1-yMg_yO₂ system upon deintercalation:electrochemical, electronic properties and ⁷Li MAS NMR studies[J]. Journal of Power Sources, 2002, 112(2):419-427.
[14] GENG F, SHEN M, HU B, et al. Monitoring the evolution of local oxygen environments during LiCoO₂ charging via ex situ ¹⁷O NMR[J]. Chemical Communications, 2019, 55(52):7550-7553.
[15] SHIMODA K, MURAKAMI M, TAKAMATSU D, et al. In situ NMR observation of the lithium extraction/insertion from LiCoO₂ cathode[J]. Electrochimica Acta, 2013, 108:343-349.
[16] HU B, LOU X, LI C, et al. Reversible phase transition enabled by binary Ba and Ti-based surface modification for high voltage LiCoO₂ cathode[J]. Journal of Power Sources, 2019, 438:226954.
[17] NIEMöLLER A, JAKES P, EICHEL R A, et al. In operando EPR investigation of redox mechanisms in LiCoO₂[J]. Chemical Physics Letters, 2019, 716:231-236.
[18] TREASE N M, SEYMOUR I D, RADIN M D, et al. Identifying the distribution of Al³⁺ in LiNi_0.8Co_0.15Al_0.05O₂[J]. Chemistry of Materials, 2016, 28(22):8170-8180.
[19] LEIFER N, SRUR-LAVI O, MATLAHOV I, et al. LiNi_0.8Co_0.15Al_0.05O₂ cathode material:New insights via ⁷Li and ²⁷Al magic-angle spinning NMR spectroscopy[J]. Chemistry of Materials, 2016, 28(21):7594-7604.
[20] ZENG D, CABANA J, BRéGER J, et al. Cation ordering in Li[Ni_xMn_xCo(_1-2x)]O₂-layered cathode materials:A nuclear magnetic resonance (NMR), pair distribution function, X-ray absorption spectroscopy, and electrochemical study[J]. Chemistry of Materials, 2007, 19(25):6277-6289.
[21] HARRIS K J, FOSTER J M, TESSARO M Z, et al. Structure solution of metal-oxide Li battery cathodes from simulated annealing and lithium NMR spectroscopy[J]. Chemistry of Materials, 2017, 29(13):5550-5557.
[22] STOYANOVA R, IVANOVA S, ZHECHEVA E, et al. Correlations between lithium local structure and electrochemistry of layered LiCo_1-2xNi_xMn_xO₂ oxides:⁷Li MAS NMR and EPR studies[J]. Physical Chemistry Chemical Physics, 2014, 16(6):2499-2507.
[23] PADHI A K, NANJUNDASWAMY K S, MASQUELIER C, et al. Mapping of transition metal redox energies in phosphates with NASICON structure by lithium intercalation[J]. Journal of the Electrochemical Society, 1997, 144(8):2581-2586.
[24] PADHI A K, MANIVANNAN V, GOODENOUGH J B. Tuning the position of the redox couples in materials with NASICON structure by anionic substitution[J]. Journal of the Electrochemical Society, 1998, 145(5):1518-1520.
[25] PADHI A K, NANJUNDASWAMY K S, GOODENOUGH J B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J]. Journal of the Electrochemical Society, 1997, 144(4):1188-1194.
[26] TUCKER M C, DOEFF M M, RICHARDSON T J, et al. Hyperfine fields at the Li site in LiFePO₄-type olivine materials for lithium rechargeable batteries:A ⁷Li MAS NMR and SQUID study[J]. Journal of the American Chemical Society, 2002, 124(15):3832-3833.
[27] CABANA J, SHIRAKAWA J, CHEN G, et al. MAS NMR study of the metastable solid solutions found in the LiFePO₄/FePO₄ system[J]. Chemistry of Materials, 2010, 22(3):1249-1262.
[28] PIGLIAPOCHI R, O'BRIEN L, PELL A J, et al. When do anisotropic magnetic susceptibilities lead to large NMR shifts? exploring particle shape effects in the battery electrode material LiFePO₄[J]. Journal of the American Chemical Society, 2019, 10.1021/jacs.9b04674:10.1021/jacs.1029b04674.
[29] DAVIS L J M, HEINMAA I, ELLIS B L, et al. Influence of particle size on solid solution formation and phase interfaces in Li_0.5FePO₄ revealed by ³¹P and ⁷Li solid state NMR spectroscopy[J]. Physical Chemistry Chemical Physics, 2011, 13(11):5171-5177.
[30] LI C, SHEN M, LOU X, et al. Unraveling the redox couples of VIII/VIV mixed-valent Na₃V₂(PO₄)₂O_1.6F_1.4 cathode by parallel-mode EPR and in situ/Ex situ NMR[J]. The Journal of Physical Chemistry C, 2018, 122(48):27224-27232.

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