烧结温度对锂离子电池负极材料Li4Ti5O12性能的影响

亢静锐; 董桂霞; 李雷; 李宗峰; 杨双娟

doi:10.19591/j.cnki.cn11-1974/tf.2019.02.010

烧结温度对锂离子电池负极材料Li₄Ti₅O₁₂性能的影响

doi: 10.19591/j.cnki.cn11-1974/tf.2019.02.010

亢静锐^{1, 2, 3},
董桂霞^{1, 2, 3, ,},
李雷^{1, 2, 3},
李宗峰^{1, 2, 3},
杨双娟^{1, 2, 3}

1.
华北理工大学材料科学与工程学院, 唐山 063210
2.
河北省无机非金属材料重点实验室，唐山 063210
3.
唐山市环境功能材料重点实验室, 唐山 063210

基金项目:

国家国际科技合作计划资助项目 2014DFR50570

详细信息

通讯作者:
董桂霞, E-mail: dgx6608@126.com

中图分类号: TM912
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出版历程
- 收稿日期: 2018-06-22
- 刊出日期: 2019-04-27

Influence of sintering temperature on the properties of Li4Ti5O12 anode material for lithium-ion batteries

KANG Jing-rui^{1, 2, 3},
DONG Gui-xia^{1, 2, 3
, ,},
LI Lei^{1, 2, 3},
LI Zong-feng^{1, 2, 3},
YANG Shuang-juan^{1, 2, 3}

1.
School of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, China
2.
Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, Tangshan 063210, China
3.
Key Laboratory of Environment Functional Materials of Tangshan City, Tangshan 063210, China

More Information

Corresponding author: DONG Gui-xia, E-mail: dgx6608@126.com

摘要

摘要: 采用钛酸四丁酯为钛源、一水合氢氧化锂为锂源，利用水热法制备锂离子电池负极材料Li₄Ti₅O₁₂（LTO），研究了水热后不同烧结温度对LTO相组成、微观形貌及电化学性能的影响。结果表明：当煅烧温度分别为500、550、600、650、700℃时，烧结LTO均为尖晶石型；500、550、600℃烧结LTO的微观形貌为纳米片状结构，当温度升高到650℃时，LTO出现纳米棒状结构，随着温度继续升高，LTO在700℃时生成较厚的纳米片状结构；当烧结温度为650℃时，LTO的比表面积为94.5907 m²·g^-1，气孔体积为0.9663 mL·g^-1，此时Li₄Ti₅O₁₂的放电比容量达到最大值240 mAh·g^-1；电流密度100 mA·g^-1、循环260次条件下，LTO容量保持率达96.45%，电流密度为1和2 A·g^-1、循环1000次条件下，LTO容量保持率达92.97%和77.21%。
- 锂离子电池 /
- 负极材料 /
- 烧结温度 /
- 显微结构 /
- 电化学性能
Abstract: The Li₄Ti₅O₁₂ (LTO) anode materials for lithium-ion batteries were prepared by hydrothermal method in this paper, using tetrabutyl titanate as the titanium source and lithium hydroxide monohydrate as the lithium source. The influence of sintering temperature on the phase composition, microstructures, and electrochemical properties of LTO was investigated. The results show that the spinel LTO is formed at 500, 550, 600, 650, and 700℃, respectively. The microstructures of LTO are present as the nanosheets sintered at 500, 550, and 600℃, the nanorods sintered at 650℃, and the thicker nonosheets sintered at 700℃. The LTO exhibits the high specific surface area of 94.5907 m²·g^-1, the good pore volume of 0.9663 mL·g^-1, and the highest initial discharge capacity of 240 mAh·g^-1 sintered at 650℃. Additionally, the LTO has an excellent cycling performance with capacity retention ratio of 96.45% after 260 cycles at 100 mA·g^-1, and the capacity retention ratio of 92.97% and 77.21% after 1000 cycles at 1 and 2 A·g^-1, respectively.
- lithium ion battery /
- anode material /
- sintering temperature /
- microstructure /
- electrochemical property

HTML全文

图 1 LTO样品X射线衍射图谱：（a）不同烧结温度；（b）（111）晶面局部放大图

Figure 1. XRD patterns of LTO samples: (a) sintered at different temperatures; (b) partial enlarged detail of (111) lattice plane

下载: 全尺寸图片幻灯片

图 2 不同烧结温度样品的扫描电子显微形貌：（a）500 ℃；（b）550 ℃；（c）600 ℃；（d）650 ℃；（e）700 ℃

Figure 2. SEM images of LTO samples sintered at different temperatures: (a) 500 ℃; (b) 550 ℃; (c) 600 ℃; (d) 650 ℃; (e) 700 ℃

下载: 全尺寸图片幻灯片

图 3 不同烧结温度LTO样品的N₂吸附-脱附等温线和孔径分布图

Figure 3. N₂ desorption-sorption isotherms and pore diameter distribution of LTO samples sintered at different temperatures

下载: 全尺寸图片幻灯片

图 4 不同烧结温度下LTO电极倍率性能图：（a）首次充放电曲线；（b）20~4000 mA·g^-1电流密度下充放电曲线

Figure 4. LTO electrodes rate performance at different sintering temperatures: (a) first charge/discharge capacities curve; (b) charge‒discharge capacities curve at 20 to 4000 mA g^-1

下载: 全尺寸图片幻灯片

图 5 LTO电极循环伏安曲线：（a）不同烧结温度LTO循环伏安曲线；（b）不同扫描速率下650 ℃烧结LTO循环伏安曲线

Figure 5. CV curves of LTO electrodes: (a) sintered at different sintering temperatures; (b) sintered at 650 ℃ in different scan rates

下载: 全尺寸图片幻灯片

图 6 不同烧结温度LTO电极的电化学阻抗图

Figure 6. Nyquist plots of LTO electrodes sintered at different sintering temperatures

下载: 全尺寸图片幻灯片

图 7 650 ℃烧结LTO电极充放电过程电化学平台曲线

Figure 7. Galvanostatic voltage profile of LTO electrode sintered at 650 ℃ in charge/discharge process

下载: 全尺寸图片幻灯片

图 8 LTO电极的循环性能和库伦效率：（a）100 mA·g^-1；（b）1和2 A·g^-1

Figure 8. Cycling performance and coulombic efficiency of electrodes: (a) 100 mA·g^-1; (b) 1 and 2 A·g^-1

下载: 全尺寸图片幻灯片

表 1 不同烧结温度下LTO样品的比表面积和孔体积

Table 1. Specific surface area and pore volume of LTO samples sintered at different temperatures

温度/℃	比表面积/(m²·g^-1)	孔体积/(mL·g^-1)
500	37.1633	0.2552
550	71.3419	0.8075
600	85.3326	0.8623
650	94.5907	0.9663
700	45.8839	0.4178

下载: 导出CSV

表 2 不同烧结温度下不同电流密度时LTO样品的放电比容量

Table 2. Discharge capacities of LTO samples sintered at different temperatures in different current densities

温度/℃	放电比容量/(mAh·g^-1)
温度/℃	20 mA·g^-1	100 mA·g^-1	500 m A·g^-1	1 A·g^-1	2 A·g^-1	4 A·g^-1
500	142.0	112.9	95.8	86.7	72.7	56.7
550	164.2	141.1	125.1	115.9	103.3	83.4
600	222.4	175.1	152.0	143.6	133.5	119.0
650	240.0	203.8	190.1	184.3	172.6	150.0
700	231.1	177.1	159.6	147.0	133.4	129.3

下载: 导出CSV

表 3 不同烧结温度下电解液电阻（R_E）和电荷迁移电阻（R_CT）数值

Table 3. Electrolyte resistance (R_E) and charge transfer resistance (R_CT) at different sintering temperatures

温度/℃	R_E/Ω	R_CT/Ω
500	2.71	211.29
550	2.10	127.30
600	4.39	192.01
650	1.80	69.20
700	2.36	93.04

下载: 导出CSV

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