钛酸锂负极的相分离机制

卢侠; 陈伟鑫

doi:10.6054/j.jscnun.2020054

钛酸锂负极的相分离机制

卢侠^,,
陈伟鑫

中山大学材料学院，广州 510006

基金项目:

国家重点研发计划项目 2019YFA0705700

国家自然科学基金项目 11704019

详细信息

通讯作者:
卢侠，教授，Email:luxia3@mail.sysu.edu.cn

中图分类号: O64
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- 文章访问数: 1673
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出版历程
- 收稿日期: 2020-03-15
- 网络出版日期: 2020-09-03
- 刊出日期: 2020-08-24

Phase Separation in Li₄Ti₅O₁₂ Anode for Li-Ion Batteries

LU Xia^,,
CHEN Weixin

School of Materials, Sun Yat-sen University, Guangzhou 510006, China

摘要

摘要: 尖晶石钛酸锂(Li₄Ti₅O₁₂)作为锂离子电池负极材料具有长寿命、高稳定性的特点，是高功率锂离子电池的理想选择，对发展电动汽车以及智能电网有重要意义.结合球差校正透射电镜(STEM)、电子能量损失谱(EELS)和理论计算，在原子尺度观测到了尖晶石钛酸锂(Li₄Ti₅O₁₂)的结构，实现了对脱嵌锂过程的直接观测与表征.在锂化过程中，出现一个近似理想的异质界面(Li₄Ti₅O₁₂/Li₇Ti₅O₁₂)，界面两侧Ti离子呈不同价态分布(Ti³⁺/Ti⁴⁺).而随着锂离子在材料中的嵌入和脱出，TiO₆八面体里面的Ti—O键会产生相应的收缩或拉伸(“呼吸”模型)，而这种键长的变化直接导致材料在不同区域的电子电导率产生质的变化(由绝缘体的Li₄Ti₅O₁₂向近似导体的Li₇Ti₅O₁₂转变)，而基本不影响材料的离子电导率，这是材料具有优良倍率性能的重要条件.借助原子分辨的EELS分析研究锂化以后的Li₇Ti₅O₁₂表面, 观测到材料表面的Ti³⁺自发氧化成Ti⁴⁺，这个电荷转移过程可以诱导电极材料界面上的副反应，可以合理解释钛酸锂电池产气的原因.进一步将钛酸锂电池用于储钠研究发现了晶格中存在Li₄Ti₅O₁₂/Li₇Ti₅O₁₂/Na₆LiTi₅O₁₂三相分离机制，深化了对电极材料过程动力学的认识.这些重要研究结果为钛酸锂的工业化应用提供了重要的结构基础与理论指导.
- 钛酸锂 /
- 相分离 /
- 呼吸模型 /
- 锂离子电池 /
- 负极
Abstract: Li₄Ti₅O₁₂ spinel has been regarded as one of the ideal anode materials for Li ion batteries and is a good candidate for developing high performance electric automobiles and smart grids for its characteristics of the long electrochemical cycle-life, high-structural stability and power density. Atomic-scale visualization of Li₄Ti₅O₁₂ spinel upon lithiation is realized using spherical aberration corrected transmission electron microscope (STEM), electron energy loss spectroscopy (EELS) and first-principles calculations. Upon lithiation, the Li₄Ti₅O₁₂ spinel transforms into the rock-salt Li₇Ti₅O₁₂ phase by developing an almost ideal hetero-interface and the Ti ions demonstrate different chemical states on the different sides of the interface. Further observation indicates that the elongation and shrinkage of Ti—O bonds in TiO₆ octahedra (breathing model) results in the fundamental changes of electronic conductivity in lithiated Li₄Ti₅O₁₂, where the insulating Li₄Ti₅O₁₂ is transformed into a quasi-conducting Li₇Ti₅O₁₂ phase. But these changes show limited influence on ionic conductivity. Using atomic-scale EELS analysis, a spontaneous oxidization process of Ti³⁺ to Ti⁴⁺ is revealed on the surface of Li₇Ti₅O₁₂ phase. This spontaneously surficial charge transfer reaction is revealed to be strongly related with the package swelling issue of Li₄Ti₅O₁₂ battery during cycling. Moreover, a three-phase separation, including the Li₄Ti₅O₁₂, Li₇Ti₅O₁₂ and Na₆LiTi₅O₁₂ phases, is found during Na insertion when Li₄Ti₅O₁₂ is employed as anode for sodium ion battery. All these important findings provide a rewarding avenue for the structural design and optimization of battery materials and lay a solid foundation for industrial application of Li₄Ti₅O₁₂ anode.
- lithium titanate /
- phase separation /
- breathing model /
- Li-ion batteries /
- anode

HTML全文

图 1 尖晶石Li₄Ti₅O₁₂的晶格结构^[10]

Figure 1. The lattice of Li₄Ti₅O₁₂ spinel^[10]

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图 2 C/20电流下的充放电曲线^[3]

注：此图来源于文献[3]的支撑材料.

Figure 2. The typical discharge/charge profile at C/20^[3]

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图 3 Li₄Ti₅O₁₂晶格沿[110]轴方向的原子尺度表征^[3]

Figure 3. The atomic-scale characterizations of Li₄Ti₅O₁₂ lattice along [110] zone axis^[3]

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图 4 不同充放电状态下Li₄Ti₅O₁₂沿[110]方向的HAADF图^[2]

Figure 4. The HAADF images of Li₄Ti₅O₁₂ in different charge and discharge conditions along [110] zone axis^[2]

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图 5 化学锂化Li₄₊_xTi₅O₁₂(x=0.15)颗粒的两相界面特性^[3]

Figure 5. The interfacial characteristics in chemically lithiated Li₄₊_xTi₅O₁₂ (x=0.15)^[3]

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图 6 中间态的锂离子迁移路径及相应的能垒^[27]

Figure 6. The Li⁺ ion migration pathways and the corresponding energy barriers in the intermediate states^[27]

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图 7 钛酸锂两相界面形成的双电层^[28]

Figure 7. The double charge layers formed between the two phase-interfaces of lithium titanate^[28]

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图 8 Ti的L_{2, 3}边EELS谱图^[3]

Figure 8. The EELS profiles of Ti L_{2, 3} edges^[3]

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图 9 Li₄Ti₅O₁₂和Li_3.5Ca_0.5Ti₅O₁₂优化后的原子结构和能带图^[37]

Figure 9. The optimized atomic structures and band graphs of Li₄Ti₅O₁₂ and Li_3.5Ca_0.5Ti₅O₁₂^[37]

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图 10 Li₄Ti₅O₁₂的高压非晶化^[49]

Figure 10. The pressure-induced amorphization of Li₄Ti₅O₁₂^[49]

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图 11 不同偏压下的Li_4-xTi₅O_12-y的STEM图像、氧原子移动方向及线扫描图^[50]

Figure 11. The STEM images, oxygen atomic shift and the line profiles of Li_4-xTi₅O_12-y under different bias^[50]

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图 12 Li₄Ti₅O₁₂不同表面结构的HAADF图^[2]

注：A图为(110)面; B图为Li—Ti乱序的(110)面; C图为(111)面; D图为(121)面; E图为(110)面.

Figure 12. The HAADF images of different surficial structures of Li₄Ti₅O₁₂^[2]

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图 13 循环过程电压曲线图及表面重构形成示意图^[1]

Figure 13. The schematic illustration of voltage profile evolution during cycles and the formation of relaxed surface zone^[1]

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图 14 Li₇Ti₅O₁₂(110)晶面的EELS谱^[2]

Figure 14. The EELS spectra of Li₇Ti₅O₁₂ (110) plane^[2]

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图 15 C/10电流下不同粘结剂的Li₄Ti₅O₁₂电极的充放电曲线及循环性能^[10]

Figure 15. The charge/discharge curves and the cyding performance of Li₄Ti₅O₁₂ electrode with different binders at C/10^[10]

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图 16 C/10电流下不同粘结剂的Li₄Ti₅O₁₂电极的同步辐射原位XRD谱^[10]

Figure 16. The in-situ synchrotron XRD spectra of Li₄Ti₅O₁₂ electrode with different binders at C/10^[10]

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图 17 半电化学钠化Li₄Ti₅O₁₂颗粒的STEM图、ABF及ABF衬度线扫描图^[10]

注：A~I分别为Na₆LiTi₅O₁₂、Li₄Ti₅O₁₂、Li₇Ti₅O₁₂的HAADF、ABF及ABF衬度线扫描图; J为相界面附近的ABF图; K、L分别为Li₄Ti₅O₁₂/Li₇Ti₅O₁₂和Na₆LiTi₅O₁₂/Li₄Ti₅O₁₂的界面线扫描图.

Figure 17. The STEM images of half-electrochemical sodiated Li₄Ti₅O₁₂ particle, ABF images and ABF line profiles^[10]

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表 1 Li₄Ti₅O₁₂/Li₇Ti₅O₁₂超晶胞中不同锂离子构型的总能量计算值^[3]

Table 1 The calculated total energy of different Li ion arrangements in Li₄Ti₅O₁₂/Li₇Ti₅O₁₂ supercell^[3]

构型	Li₄Ti₅O₁₂				Li₇Ti₅O₁₂
构型	N(8a)	N(16c)	N(16d)	总能量/eV	N(8a)	N(16c)	N(16d)	总能量/eV
1	6	0	2	0	0	12	2	0
2	5	1	2	1.356	1	11	2	2.237
3	4	2	2	3.584	2	10	2	5.560
4	3	3	2	4.912	3	9	2	6.962
5	2	4	2	4.478	4	8	2	7.412
6	1	5	2	3.321	5	7	2	8.441
7	0	6	2	3.262	6	6	2	9.468
注：N为不同位点的原子数.

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表 2 Li₇Ti₅O₁₂中Ti离子的Bader电荷分析^[3]

Table 2 The Bader atomic charge analysis of the Ti ions in Li₇Ti₅O₁₂ supercell^[3]

GGA结果			GGA+U (U_eff=4.5 eV)结果
电荷/e	D_min/nm	V/(×10^-3 nm³)	电荷/e	D_min/nm	V/(×10^-3 nm³)
1.494 2	0.670 8	4.273 3	1.382 9	0.654 3	4.201 1
1.499 1	0.667 5	4.294 5	1.350 9	0.541 8	4.062 8
1.508 6	0.673 5	4.278 6	1.383 7	0.678 4	4.168 3
1.496 2	0.614 0	4.256 2	1.358 7	0.655 6	4.083 3
1.562 5	0.636 7	4.492 8	1.754 5	0.573 0	5.670 9
1.509 3	0.673 5	4.254 8	1.748 3	0.607 3	5.709 3
1.622 6	0.617 0	4.696 3	1.755 4	0.617 4	5.568 2
1.628 2	0.672 2	4.776 9	1.759 5	0.631 5	5.727 1
1.576 0	0.680 5	4.804 7	1.776 5	0.632 8	5.710 6

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