不同钛源制备钛酸锂负极材料及其性能研究

蒋鑫玉; 马光强; 朱芩枚; 田从学

doi:10.7513/j.issn.1004-7638.2023.04.011

不同钛源制备钛酸锂负极材料及其性能研究

doi: 10.7513/j.issn.1004-7638.2023.04.011

攀枝花学院生物与化学工程学院, 四川攀枝花617000

基金项目: 绿色催化四川省高校重点实验室开放基金项目（编号： LYJ1908）。

详细信息

作者简介:
马光强，1977年出生，男，四川泸县人，硕士，教授，通讯作者，主要研究方向为钒钛新能源材料，E-mail：magq3218@163.com

通讯作者:
马光强，1977年出生，男，四川泸县人，硕士，教授，通讯作者，主要研究方向为钒钛新能源材料，E-mail：magq3218@163.com

中图分类号: TF823,TM911
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出版历程
- 收稿日期: 2022-08-26
- 刊出日期: 2023-08-30

Preparation and properties of lithium titanate anode materials with different titanium sources

School of Biological and Chemical Engineering, Panzhihua University, Panzhihua 617000, Sichuan, China

摘要

摘要: 通过高温固相法制备球形Li₄Ti₅O₁₂负极材料，探究了采用不同钛源所制备的Li₄Ti₅O₁₂的性能差异。通过XRD、SEM对制备的材料进行结构及形貌的表征，同时将合成的材料进行电化学测试。结果表明，分别以纳米TiO₂(P40)、工业H₂TiO₃、含铁工业H₂TiO₃为钛源制备的Li₄Ti₅O₁₂材料t-LTO、h-LTO、f-LTO在较低倍率0.2 C下的放电比容量分别为170.0、156.3、150.7 mAh/g，在较高倍率5 C下的放电比容量分别为91.9、93.0、26.7 mAh/g。在1 C下充放电循环100次后容量保持率分别为97.4%、97.3%、94.6%。以纳米TiO₂及工业H₂TiO₃为钛源制备得到的Li₄Ti₅O₁₂具有较好的电化学性能，因此可用较为纯净的工业H₂TiO₃为钛源代替价格高昂的TiO₂制备Li₄Ti₅O₁₂负极材料。
- 锂离子电池 /
- 负极材料 /
- Li₄Ti₅O₁₂ /
- 高温固相法 /
- 钛源
Abstract: Spherical Li₄Ti₅O₁₂ anode materials were prepared by high temperature solid phase method, and the effects of different titanium sources on the properties of Li₄Ti₅O₁₂ anode materials were investigated. The structure and morphology of the prepared materials were characterized by XRD and SEM, and the synthesized materials were tested by electrochemical method. The results show that the discharge specific capacities of t-LTO, h-LTO and f-LTO prepared with nano TiO₂(P40), industrial H₂TiO₃ and industrial H₂TiO₃ containing iron are 170.0, 156.3 and 150.7 mAh/g at lower charge/discharge rate of 0.2 C, respectively. And the discharge specific capacities at the higher rate of 5 C are 91.9, 93.0 and 26.7 mAh/g, respectively. After 100 cycles of charging and discharging at 1 C, the capacity retention rates are 97.4%, 97.3% and 94.6%, respectively. Li₄Ti₅O₁₂ prepared with nano TiO₂ and industrial H₂TiO₃ has good electrochemical performance, so relatively pure industrial H₂TiO₃ can be used as a substitute for expensive TiO₂ to prepare Li₄Ti₅O₁₂ anode materials.
- lithium ion battery /
- anode materials /
- Li₄Ti₅O₁₂ /
- high temperature solid phase method /
- titanium sources

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图 1 t-LTO、h-LTO及f-LTO的XRD衍射图谱

Figure 1. XRD patterns of t-LTO, h-LTO and f-LTO

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图 2 不同钛源制备Li₄Ti₅O₁₂微球的SEM形貌

Figure 2. SEM images of Li₄Ti₅O₁₂ microspheres prepared with different titanium sources

(a) t-LTO; (b)h-LTO; (c)f-LTO

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图 3 (a)t-LTO、h-LTO和f-LTO在不同速率下的倍率性能; (b) t-LTO、h-LTO和f-LTO在1 C下的循环性能；(c) t-LTO、h-LTO和f-LTO在0.5 mV/s下的CV曲线; (d) t-LTO、h-LTO和f-LTO的EIS曲线

Figure 3. (a) Magnification performance diagrams of t-LTO, h-LTO and f-LTO at different rates, (b) Cycle performance diagrams of t-LTO, h-LTO and f-LTO at 1 C, (c) CV curves of t-LTO, h-LTO and f-LTO at 0.5 mV/s and (d) EIS curves of t-LTO, h-LTO and f-LTO

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参考文献(14)

[1]	Li Chunxiao. Research progress of anode materials for lithium ion batteries[J]. Advanced Materials Industry, 2017,(9):27−33. (李春晓. 锂离子电池负极材料研究进展[J]. 新材料产业, 2017,(9):27−33. Li Chunxiao. Research progress of anode materials for lithium ion batteries[J]. Advanced Materials Industry, 2017(9): 27-33.
[2]	Li Wang, Liu Jiali. Preparation and electrode formulations of lithium titanate[J]. Iron Steel Vanadium Titanium, 2019,40(2):50−54. (李旺, 刘佳丽. 钛酸锂材料的制备及电极配方研究[J]. 钢铁钒钛, 2019,40(2):50−54. doi: 10.7513/j.issn.1004-7638.2019.02.008 Li Wang, Liu Jiali. Preparation and electrode formulations of lithium titanate[J]. Iron Steel Vanadium Titanium, 2019, 40(2): 50-54. doi: 10.7513/j.issn.1004-7638.2019.02.008
[3]	Shi Ying, Wen Lei, Wu Minjie, et al. Applications of the carbon materials on lithium titanium oxide as anode for lithium ion batteries[J]. Progress In Chemistry, 2017,29(1):149−161. (石颖, 闻雷, 吴敏杰, 等. 碳材料在钛酸锂负极材料中的应用[J]. 化学进展, 2017,29(1):149−161. Shi Ying, Wen Lei, Wu Minjie, et al. Applications of the carbon materials on lithium titanium oxide as anode for lithium ion batteries[J]. Progress In Chemistry, 2017, 29(1): 149-161.
[4]	Li Wang, Liu Jiali, Zhou Lan. Dynamic and frontier of modifications of Li₄Ti₅O₁₂ anode material[J]. Iron Steel Vanadium Titanium, 2018,39(4):11−16. (李旺, 刘佳丽, 周兰. 国内外钛酸锂负极材料改性研究动态与前沿[J]. 钢铁钒钛, 2018,39(4):11−16. Li Wang, Liu Jiali, Zhou Lan. Dynamic and frontier of modifications of Li₄Ti₅O₁₂ anode material[J]. Iron Steel Vanadium Titanium, 2018, 39(4): 11-16.
[5]	Meng Weiwei. Preparation of Li₄Ti₅O₁₂/C composite and its application to anode material of high rate lithium-ion battery[J]. Iron Steel Vanadium Titanium, 2017,38(3):52−56,77. (孟伟巍. 改性钛酸锂复合材料作为高倍率锂离子电池负极材料研究[J]. 钢铁钒钛, 2017,38(3):52−56,77. doi: 10.7513/j.issn.1004-7638.2017.03.009 Meng Weiwei. Preparation of Li₄Ti₅O₁₂ /C composite and its application to anode material of high rate lithium-ion battery[J]. Iron Steel Vanadium Titanium, 2017, 38(3): 52-56, 77. doi: 10.7513/j.issn.1004-7638.2017.03.009
[6]	Ma Guangqiang. Lithium ion battery cathode material Li₄Ti₅O₁₂ prepared by high-temperature solid method using metatitanic acid[J]. Electronic Components and Materials, 2016,35(3):19−21. (马光强. 偏钛酸高温固相法制备锂离子电池负极材料尖晶石Li₄Ti₅O₁₂[J]. 电子元件与材料, 2016,35(3):19−21. Ma Guangqiang. Lithium ion battery cathode material Li₄Ti₅O₁₂ prepared by high-temperature solid method using metatitanic acid[J]. Electronic Components And Materials, 2016, 35(3): 19-21.
[7]	Yu Xiaolin, Wu Xianming, Li Yehua, et al. Preparation and electrochemical performance of Li₄Ti₅O₁₂ anode material by high-temperature solid-state method[J]. Guangdong Chemical Industry, 2017,44(7):61−63. (于小林, 吴显明, 李叶华, 等. 高温固相法合成Li₄Ti₅O₁₂及其电化学性能研究[J]. 广东化工, 2017,44(7):61−63. doi: 10.3969/j.issn.1007-1865.2017.07.028 Yu Xiaolin, Wu Xianming, Li Yehua, et al. Preparation and electrochemical performance of Li₄Ti₅O₁₂ anode material by high-temperature solid-state method[J]. Guangdong Chemical Industry, 2017, 44(7): 61-63. doi: 10.3969/j.issn.1007-1865.2017.07.028
[8]	Liu Wei, Zhang Ni, Bai Yang, et al. Synthesis of lithium-ion battery anode material Li₄Ti₅O₁₂ by the microwave assisted sol–gel method[J]. Journal of the Chinese Ceramic Society, 2010,38(12):2279−2283. (刘微, 张妮, 白阳, 等. 微波辅助溶胶-凝胶法合成锂离子电池负极材料Li₄Ti₅O₁₂[J]. 硅酸盐学报, 2010,38(12):2279−2283. Liu Wei, Zhang Ni, Bai Yang, et al. Synthesis of lithium-ion battery anode material Li₄Ti₅O₁₂ by the microwave assisted sol–gel method[J]. Journal of the Chinese Ceramic Society, 2010, 38(12): 2279-2283.
[9]	Lian Tianrou, Lu Yuxiao, Wu Bing, et al. Preparation and transport property of nano-Li₄Ti₅O₁₂ anode materials[J]. Journal of Materials Engineering, 2021,49(3):59−66. (廉恬柔, 卢玉晓, 吴冰, 等. 纳米级Li₄Ti₅O₁₂负极材料的制备及其输运特性[J]. 材料工程, 2021,49(3):59−66. Lian Tianrou, Lu Yuxiao, Wu Bing, et al. Preparation and transport property of nano-Li₄Ti₅O₁₂ anode materials[J]. Journal of Materials Engineering, 2021, 49(3): 59-66.
[10]	You Yahua, Zhang Yang, Li Xueliang, et al. Hydrothermal synthesis and electrochemical properties of Li₄Ti₅O₁₂ anode material[J]. Metallic Functional Materials, 2013,20(3):28−31. (尤亚华, 张杨, 李学良, 等. 水热法制备Li₄Ti₅O₁₂负极材料及其电化学性能[J]. 金属功能材料, 2013,20(3):28−31. You Yahua, Zhang Yang, Li Xueliang, et al. Hydrothermal synthesis and electrochemical properties of Li₄Ti₅O₁₂ anode material[J]. Metallic Functional Materials, 2013, 20(3): 28-31.
[11]	Yu Xiaolin, Wu Xianming, Ding Xinxiong, et al. Preparation and electrochemical performance of Li₄Ti₅O₁₂ nanosheets by hydrothermal method[J]. Modern Chemical Industry, 2018,38(2):83−86. (于小林, 吴显明, 丁心雄, 等. 水热法制备纳米片钛酸锂及其性质研究[J]. 现代化工, 2018,38(2):83−86. doi: 10.16606/j.cnki.issn0253-4320.2018.02.019 Yu Xiaolin, Wu Xianming, Ding Xinxiong, et al. Preparation and electrochemical performance of Li₄Ti₅O₁₂ nanosheets by hydrothermal method[J]. Modern Chemical Industry, 2018, 38(2): 83-86. doi: 10.16606/j.cnki.issn0253-4320.2018.02.019
[12]	Lv Jing, Zuo Yuxiang, Huang Bing, et al. Synthesis and properties of lithium titanate anode material prepared by different sizes of titanium dioxide[J]. Chemical Engineer, 2016,30(7):84−85. (吕婧, 左玉香, 黄兵, 等. 不同粒径的纳米二氧化钛合成钛酸锂负极材料[J]. 化学工程师, 2016,30(7):84−85. doi: 10.16247/j.cnki.23-1171/tq.20160784 Lv Jing, Zuo Yuxiang, Huang Bing, et al. Synthesis and properties of lithium titanate anode material prepared by different sizes of titanium dioxide[J]. Chemical Engineer, 2016, 30(7): 84-85. doi: 10.16247/j.cnki.23-1171/tq.20160784
[13]	周若. 钛酸锂的制备及改性研究[D]. 唐山: 华北理工大学, 2020. Zhou Ruo. Preparation and modification of lithium titanate[D]. Tangshan: North China University of Science and Technology, 2020.
[14]	Yuan T, Tan Z, Ma C, et al. Challenges of spinel Li₄Ti₅O₁₂ for lithium‐ion battery industrial applications[J]. Advanced Energy Materials, 2017,7(12):1601625. doi: 10.1002/aenm.201601625