靜電紡絲法制備空心鈦酸鋰材料

王瑜東; 楊凱; 張明杰; 李建玲; 高飛; 劉皓; 耿萌萌

doi:10.13374/j.issn2095-9389.2019.01.012

靜電紡絲法制備空心鈦酸鋰材料

doi: 10.13374/j.issn2095-9389.2019.01.012

王瑜東^{1, 2},
楊凱^1, ,,
張明杰¹,
李建玲²,
高飛¹,
劉皓¹,
耿萌萌¹

1.
中國電力科學研究院有限公司新能源與儲能運行控制國家重點實驗室, 北京 100192
2.
北京科技大學冶金與生態工程學院, 北京 100083

基金項目:

國家自然科學基金資助項目 51407166

國網公司科技資助項目 DG71-16-015

詳細信息

通訊作者:
楊凱, E-mail: yangkai@epri.sgcc.com.cn

中圖分類號: TG142.71
計量
- 文章訪問數: 985
- HTML全文瀏覽量: 572
- PDF下載量: 33
- 被引次數: 0
出版歷程
- 收稿日期: 2017-12-20
- 刊出日期: 2019-01-01

Fabrication of hollow lithium titanate material by electrospinning

1.
State Key Laboratory of Operation and Control of Renewable Energy & Storage Systems, China Electric Power Research Institute. Beijing 100192, China
2.
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: YANG Kai, E-mail: yangkai@epri.sgcc.com.cn

摘要

摘要: 為進一步提升鈦酸鋰材料的性能, 本文在傳統靜電紡絲技術的基礎上, 將紡絲噴頭改進成內外嵌套的同軸噴頭, 以兩種溶液的形式進行同軸共紡, 得到了具有空心結構的鈦酸鋰纖維絲.將其與傳統靜電紡絲法制備的實心結構鈦酸鋰纖維絲進行對比, 結果表明: 空心鈦酸鋰材料粒度均一、無團聚現象, 材料具有明顯的空心結構, 結晶性能良好, 比表面積是實心結構的1.3倍.形貌結構的改善極大地提高了空心鈦酸鋰材料的電化學性能, 表現為小倍率下二者的放電比容量接近理論比容量, 但在20C倍率下空心結構的鈦酸鋰材料優于實心鈦酸鋰, 仍可達到130 mA·h·g^-1, 循環200周后容量保持率仍達98%, 具有良好的穩定性; 循環伏安和交流阻抗曲線也表明: 空心結構使得鈦酸鋰材料的極化程度減少, 電化學反應阻抗降低, 更有利于電化學反應的進行.
- 鈦酸鋰 /
- 靜電紡絲 /
- 空心結構 /
- 儲能 /
- 鋰離子電池
Abstract: Lithium titanate (Li₄Ti₅O₁₂, LTO) is an important material to be used as an anode for LIBs (Li⁺ ion battery). LTO is a zero-strain material (i.e., no structural change occurs during Li insertion/extraction). Although LTO is a very safe material that can be used as an anode material in high and low temperature environment, its rate capability is compromised by its low electronic conductivity and poor Li⁺ diffusion coefficient. In the recent years, considerable research around the world has focused on improving LTO rate performance. Efforts to achieve better electrical conduction between LTO particles have included LTO particle size control, conductive-material surface coatings, and alien ion doping. However, in this study electrochemical properties were improved by changing the morphology of LTO. Based on traditional electrospinning technology, LTO fibers with a hollow structure were produced using a nested coaxial nozzle modified from the conventional spinning nozzle and coaxial cospinning with two different solutions. A comparison of this results with those of solid LTO prepared by traditional electrospinning technology demonstrates that hollow LTO is characterized by uniform particle size and no agglomeration, along with an obvious hollow structure, clear crystal lattice stripes, and good crystallization property. The specific surface of this hollow LTO is 1.3 times than its solid counterpart. This morphological change greatly improves the electrochemical performance of the material. Although the discharge specific capacities of both the solid and hollow LTO are close to the theoretical value for small ratios, the hollow LTO is superior to its solid counterpart at 20C. The discharge specific capacity of the hollow LTO can reach 130 mA·h·g^-1 at 20C, and after 200 cycles, its capacity retention ratio remains at 98%, which suggests good stability. Cyclic voltammetry and AC impedance curves also show that the hollow structure reduces the degree of polarization and the electrochemical reaction impedance of LTO, which makes LTO more conducive to electrochemical reaction.
- lithium titanate /
- electrospinning /
- hollow structure /
- energy storage /
- lithium-ion battery

HTML全文

圖 1 空心鈦酸鋰纖維絲制備流程示意圖

Figure 1. Schematic of the simple synthetic route of hollow lithium titanate nanofibers

下載: 全尺寸圖片幻燈片

圖 2 實心鈦酸鋰材料和空心鈦酸鋰材料的X射線衍射對比圖

Figure 2. Comparison of XRD results of SLTO and HLTO

下載: 全尺寸圖片幻燈片

圖 3 實心鈦酸鋰材料(a)和空心鈦酸鋰材料(b)的掃描電鏡圖

Figure 3. SEM images of SLTO (a) and HLTO (b)

下載: 全尺寸圖片幻燈片

圖 4 空心結構鈦酸鋰的透射電鏡圖.(a)形貌圖; (b)晶格條紋圖

Figure 4. TEM images of hollow lithium titanate: (a)topography; (b)lattice fringe pattern

下載: 全尺寸圖片幻燈片

圖 5 實心鈦酸鋰材料和空心鈦酸鋰材料比體積對比圖

Figure 5. Specific volume curves of SLTO and HLTO

下載: 全尺寸圖片幻燈片

圖 6 實心鈦酸鋰材料和空心鈦酸鋰材料電池的循環伏安曲線

Figure 6. Cyclic voltammetry curves of SLTO and HLTO

下載: 全尺寸圖片幻燈片

圖 7 實心鈦酸鋰材料和空心鈦酸鋰材料電池交流阻抗圖

Figure 7. Exchange impedance spectroscopy results of SLTO and HLTO

下載: 全尺寸圖片幻燈片

圖 8 實心鈦酸鋰材料和空心鈦酸鋰材料電池的放電曲線圖.(a)不同倍率比容量圖; (b)高倍率充放電循環圖

Figure 8. Charge-discharge curve graphs for SLTO and HLTO: (a)specific capacity of different rates; (b)charge and discharge cycling curve at high rate

下載: 全尺寸圖片幻燈片

表 1 實心鈦酸鋰材料和空心鈦酸鋰材料比表面積值

Table 1. Specific surface data of SLTO and HLTO

樣品種類	比表面積/(m²·g^-1)
實心鈦酸鋰材料	8.502
空心鈦酸鋰材料	11.156

下載: 導出CSV

表 2 實心鈦酸鋰材料和空心鈦酸鋰材料循環伏安對比

Table 2. Comparison of cyclic voltammetries of SLTO and HLTO

樣品	φ_a/V	φ_c/V	(φ_a-φ_c)/mV
空心鈦酸鋰材料	1.6229	1.5228	100.1
實心鈦酸鋰材料	1.6376	1.5048	132.8

下載: 導出CSV

表 3 實心鈦酸鋰材料和空心鈦酸鋰材料電池的交流阻抗阻值

Table 3. Fitted EIS data of SLTO and HLTO

阻抗值	R_s/Ω	R_ct/Ω
實心鈦酸鋰材料	6.02	70.26
空心鈦酸鋰材料	5.38	38.14

下載: 導出CSV

259luxu-164

參考文獻(15)

[1]	Liu Y X, Hou X Z, Li L X, et al. Application of lithium titanate battery in industrialization of urban transit electric vehicles. Smart Grid, 2014, 4: 280 劉永相, 侯興哲, 李林霞, 等. 鈦酸鋰電池在城市公交電動產業化中的應用. 智能電網, 2014, 4: 280
[2]	Huang R F. Analysis for the applications of lithium titanate battery in the MW-class energy storage systems. Energy Storage Sci Technol, 2015, 4(3): 290 doi: 10.3969/j.issn.2095-4239.2015.03.008 黃任飛. 鈦酸鋰電池在兆瓦級儲能系統中的應用分析. 儲能科學與技術, 2015, 4(3): 290 doi: 10.3969/j.issn.2095-4239.2015.03.008
[3]	Ni H F, Fan L Z. Developments on spinel Li₄Ti₅O₁₂ as anode material. J Chin Ceram Soc, 2012, 40(4): 548 https://www.cnki.com.cn/Article/CJFDTOTAL-GXYB201204016.htm 倪海芳, 范麗珍. 尖晶石型Li₄Ti₅O₁₂負極材料的研究進展. 硅酸鹽學報, 2012, 40(4): 548 https://www.cnki.com.cn/Article/CJFDTOTAL-GXYB201204016.htm
[4]	Li Z Y, Li J L, Zhao Y G, et al. Influence of cooling mode on the electrochemical properties of Li₄Ti₅O₁₂ anode materials for lithium-ion batteries. Ionics, 2016, 22(6): 789 doi: 10.1007/s11581-015-1610-0
[5]	Deptu?a A, ?ada W, Olczak T, et al. Preparation of lithium titanate by sol-gel method. Nukleonika, 2001, 46(3): 95
[6]	Zhang Y Y, Wang D, Zhang C M, et al. Research progress on Li₄Ti₅O₁₂ as anode material for Li-ion battery synthesized by hydrothermal method. Chin J Power Sources, 2014, 38(11): 2202 doi: 10.3969/j.issn.1002-087X.2014.11.070 張遙遙, 王丹, 張春明, 等. 水熱法制備鋰離子電池負極材料Li₄Ti₅O₁₂研究進展. 電源技術, 2014, 38(11): 2202 doi: 10.3969/j.issn.1002-087X.2014.11.070
[7]	Liu W, Zhang N, Bai Y, et al. Synthesis of lithium-ion battery anode material Li₄Ti₅O₁₂ by the microwave assisted sol-gel method. J Chin Ceram Soc, 2010, 38(12): 2279 https://www.cnki.com.cn/Article/CJFDTOTAL-GXYB201012014.htm 劉微, 張妮, 白陽, 等. 微波輔助溶膠-凝膠法合成鋰離子電池負極材料Li₄Ti₅O₁₂. 硅酸鹽學報, 2010, 38(12): 2279 https://www.cnki.com.cn/Article/CJFDTOTAL-GXYB201012014.htm
[8]	Gong X, Yang J L, Jiang Y L, et al. Application of electrospinning technique in power lithium-ion batteries. Prog Chem, 2014, 26(1): 41 http://en.cnki.com.cn/Article_en/CJFDTOTAL-HXJZ201401005.htm
[9]	Li X L, Zhang Y, You Y H, et al. Ionothermal synthesis and electrochemical properties of Li₄Ti₅O₁₂ anode material. J Chin Ceram Soc, 2013, 41(1): 7 https://www.cnki.com.cn/Article/CJFDTOTAL-GXYB201301003.htm 李學良, 張楊, 尤亞華, 等. 離子熱法制備Li₄Ti₅O₁₂負極材料及其電化學性能. 硅酸鹽學報, 2013, 41(1): 7 https://www.cnki.com.cn/Article/CJFDTOTAL-GXYB201301003.htm
[10]	Haridas A K, Sharma C S, Rao T N. Electrochemical performance of lithium titanate submicron rods synthesized by sol-gel/electrospinning. Electroanalysis, 2014, 26(11): 2315 doi: 10.1002/elan.201400233
[11]	Yu Q, Wang M, Chen H. Fabrication of ordered TiO₂ nanoribbon arrays by electrospinning. Mater Lett, 2010, 64(3): 428 doi: 10.1016/j.matlet.2009.11.039
[12]	Zhang W H, Liu C K, Sun R J, et al. Effect of electrospinning parameters on diameter and orientation of nanofiber. Synth Fiber China, 2011, 40(1): 38 https://www.cnki.com.cn/Article/CJFDTOTAL-HCXW201101010.htm 張娓華, 劉呈坤, 孫潤軍, 等. 靜電紡參數對納米纖維直徑及定向性的影響. 合成纖維, 2011, 40(1): 38 https://www.cnki.com.cn/Article/CJFDTOTAL-HCXW201101010.htm
[13]	Cho Y, Lee S, Lee Y, et al. Spinel-layered core-shell cathode materials for Li-ion batteries. Adv Energy Mater, 2011, 1(5): 821 doi: 10.1002/aenm.201100239
[14]	Vaseashta A. Controlled formation of multiple Taylor cones in electrospinning process. Appl Phys Lett, 2007, 90(9): 093115-1 doi: 10.1063/1.2709958
[15]	Moghe A K, Gupta B S. Co-axial electrospinning for nanofiber structures: preparation and applications. Polym Rev, 2008, 48(2): 353 doi: 10.1080/15583720802022257