非晶态磷酸锂包覆钛酸锂电极在0.01~3.00 V电压范围的性能研究

doi:10.15541/jim20200576

无机材料学报 ›› 2021, Vol. 36 ›› Issue (9): 999-1005.DOI: 10.15541/jim20200576

非晶态磷酸锂包覆钛酸锂电极在0.01~3.00 V电压范围的性能研究

王影¹(), 张文龙¹, 邢彦锋¹(), 曹苏群², 戴新义³, 李晶泽⁴()

1.上海工程技术大学机械与汽车工程学院, 上海 201620
2.淮阴工学院电子信息工程学院, 淮安 223003
3.贵州大学材料与冶金学院, 贵阳 550025
4.电子科技大学微电子学与固体电子学院, 成都 610054

收稿日期:2020-09-30 修回日期:2021-01-07 出版日期:2021-09-20 网络出版日期:2021-01-25
通讯作者: 邢彦锋, 教授. E-mail: smsmsues@163.com; 李晶泽, 教授. E-mail: lijingze@uestc.edu.cn
作者简介:王影(1978-), 女, 讲师. E-mail: wangyingcae@sues.edu.cn

Performance of Amorphous Lithium Phosphate Coated Lithium Titanate Electrodes in Extended Working Range of 0.01-3.00 V

WANG Ying¹(), ZHANG Wenlong¹, XING Yanfeng¹(), CAO suqun², DAI Xinyi³, LI Jingze⁴()

1. School of Mechanical and Automobile Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
2. Faculty of Electronic Information Engineering, Huaiyin Institute of Technology, Huaian 223003, China
3. College of Materials and Metallurgy, Guizhou University, Guiyang 550025, China
4. School of Microelectronics and Solid-state Electronics, University of Electronic Science and Technology of China, Chengdu 610054, China

Received:2020-09-30 Revised:2021-01-07 Published:2021-09-20 Online:2021-01-25
Contact: XING Yanfeng, professor. E-mail: smsmsues@163.com; LI Jingze, professor. E-mail: lijingze@uestc.edu.cn
About author:WANG Ying (1978-), female, lecturer. E-mail: wangyingcae@sues.edu.cn
Supported by:
National Natural Science Foundation of China(51575335);Program for New Century Excellent Talents in University(NCET-10-0296);Science and Technology Commission of Shanghai Municipality(16030501300);Open fund of Jiangsu Laboratory of Lake Environment Remote Sensing Technologies(JSLERS-2019-003);Open Project of Shanghai Key Laboratory of Digital Manufacture for Thin-walled Structures(2019-002)

摘要/Abstract

摘要：

长期以来, 表面包覆一直是改善锂离子电池电极材料电化学性能的有效手段。本研究采用磁控溅射法将非晶态磷酸锂包覆在Li₄Ti₅O₁₂电极片表面, 修饰后电极表面光滑, 形成了均匀的非晶态磷酸锂包覆层。在0.01-3.00 V电压范围的充放电测试结果显示, 该包覆层可显著改善电极的倍率性能和循环性能。当充放电电流密度分别为35和1750 mA∙g^-1时, 电池容量可以达到265和151 mAh∙g^-1, 远高于未包覆电池的240和22 mAh∙g^-1, 并以88 mA∙g^-1的电流密度进一步充放电200个循环后, 仍保留了238 mAh∙g^-1的高可逆容量。这是由于非晶态磷酸锂包覆层可稳定电解质界面, 保持粒子间电子通道的完整性, 并在电极表面形成交联离子导电网络, 使得改性电极的倍率性能和循环稳定性显著提高。

关键词: 钛酸锂, 磷酸锂, 阳极, 锂离子电池, 磁控溅射

Abstract:

Surface coating has long been an effective means to improve the electrochemical performance of electrode materials for Li-ion batteries. In this study, the traditional micron-sized Li₄Ti₅O₁₂ anodes are coated with amorphous lithium phosphate by radio frequency (RF) magnetron sputtering. The characterized morphology indicates that the electrodes are covered by a thin amorphous lithium phosphate coating layer, showing a very smooth surface. Both the rate performance and cycle performance of the electrodes are enhanced markedly by the coating layer in the voltage range of 0.01-3.00 V. When the discharge-charge currents are 35 and 1750 mA∙g^-1, the capacities are elevated to 265 and 151 mAh∙g^-1, respectively, which are higher than those of the uncoated ones (240 and 22 mAh∙g^-1). After further discharge-charged for 200 cycles at 88 mA∙g^-1, the coated electrodes still maintain a high reversible capacity of 238 mAh∙g^-1. This result clearly suggests that the thin layer can stabilize the solid electrolyte interface, maintain the integrity of the interparticle electronic passage and form a cross-linked ionic conducting network for Li₄Ti₅O₁₂ grains on the surface.

Key words: lithium titanate, amorphous lithium phosphate, anode, lithium-ion battery, magnetron sputtering

中图分类号:

TM912

王影, 张文龙, 邢彦锋, 曹苏群, 戴新义, 李晶泽. 非晶态磷酸锂包覆钛酸锂电极在0.01~3.00 V电压范围的性能研究[J]. 无机材料学报, 2021, 36(9): 999-1005.

WANG Ying, ZHANG Wenlong, XING Yanfeng, CAO suqun, DAI Xinyi, LI Jingze. Performance of Amorphous Lithium Phosphate Coated Lithium Titanate Electrodes in Extended Working Range of 0.01-3.00 V[J]. Journal of Inorganic Materials, 2021, 36(9): 999-1005.

图/表 11

Fig. 1 XRD patterns of pristine electrode LTOLPO00 and coated electrodes LTOLPO10, LTOLPO20 and LTOLPO40

Fig. S1 FT-IR absorption spectra of Li3PO4 sputtered on copper foil for 60 min

Fig. 2 SEM images of pristine electrode LTOLPO00 (a) and coated electrodes LTOLPO10 (b), LTOLPO20 (c), and LTOLPO40 (d)

Fig. S2 EDS result of Li4Ti5O12 electrode sputtered for 40 min (LTOLPO40)

Fig. 3 (a, c) First two discharge-charge curves at 35 mA∙g-1, 22nd discharge-charge curve at 175 mA∙g-1 and (b, d) the corresponding differential capacity plots of (a, b) pristine electrode LTOLPO00 and (c, d) coated electrode LTOLPO20

Fig. 4 (a) Rate performance and (b) long cycle performance of LTOLPO00-LTOLPO40

Fig. S3 SEM images of (a)primary electrode and (b)Li3PO4 modified electrode (LTOLPO40) after being cycled for 100 times

Fig. S4 Cycle performance and galvanostatic discharge-charge test profiles of LTOLPO60

Fig. 5 XRD patterns and (b) Raman spectra of LTOLPO00 and LTOLPO20 before and after discharge-charge tests with inset in (b) showing magnification of Raman shift at 233 cm-1

Fig. 6 EIS plots and the fitted data of (a) LTOLPO00 and (b) LTOLPO20 after discharge-charged for 10 and 100 cycles with insets showing the corresponding equivalent circuits

Table 1 Fitted data for EIS plots of LTOLPO00 and LTOLPO20 at given cycles

Sample	Cycle No.	R_s/Ω	R_f1/Ω	R_f2/Ω	R_ct/Ω
LTOLPO00	10	5	15	-	86
LTOLPO20	10	5	21	180	54
LTOLPO00	100	5	364	-	1019
LTOLPO20	100	7	25	146	216

参考文献 24

[1]	ZAGHIB K, SIMONEAU M, ARMAND M, et al. Electrochemical study of Li₄Ti₅O₁₂ as negative electrode for Li-ion polymer rechargeable batteries. Journal of Power Sources, 1999, 81-82:300-305. DOI URL
[2]	CHOI S H, KWON T, COSKUN A, et al. Highly elastic binders integrating polyrotaxanes for silicon microparticle anodes in lithium ion batteries. Science, 2017, 357(6348):279-283. DOI URL
[3]	ZHONG Z Y, OUYANG C, SHI S Q, et al. Ab initio studies on Li₄+_xTi₅O₁₂ compounds as anode materials for lithium-ion batteries. ChemPhysChem, 2008, 9(14):2104-2108. DOI URL
[4]	STENINA I A, SOBOLEV A N, YAROSLAVTSEV S, et al. Influence of iron doping on structure and electrochemical properties of Li₄Ti₅O₁₂. Electrochimica Acta, 2016, 219:524-530. DOI URL
[5]	BHATTI H S, ANJUM D H, ULLAH S, et al. Electrochemical characteristics and Li⁺ ion intercalation kinetics of dual-phase Li₄Ti₅O₁₂/Li₂TiO₃ composite in the voltage range 0-3 V. The Journal of Physical Chemistry C, 2016, 120(18):9553-9561. DOI URL
[6]	WANG Y, REN Y, DAI X Y, et al. Electrochemical performance of ZnO-coated Li₄Ti₅O₁₂ composite electrodes for lithium-ion batteries with the voltage ranging from 3 to 0.01 V. Royal Society Open Science, 2018, 5(10):180762. DOI URL
[7]	JIANG S, ZHAO B, CHEN Y, et al. Li₄Ti₅O₁₂ electrodes operated under hurdle conditions and SiO₂ incorporation effect. Journal of Power Sources, 2013, 238:356-365. DOI URL
[8]	JUNG Y S, CAVANAGH A S, RILEY L A, et al. Ultrathin direct atomic layer deposition on composite electrodes for highly durable and safe Li-ion batteries. Advanced Materials, 2010, 22(19):2172-2176. DOI URL
[9]	LI N W, YIN Y X, YANG C P, et al. An artificial solid electrolyte interphase layer for stable lithium metal anodes. Advanced Materials, 2016, 28(9):1853-1858. DOI URL
[10]	WANG Y, ZHOU A J, DAI X Y, et al. Solid-state synthesis of submicron-sized Li₄Ti₅O₁₂/Li₂TiO₃ composites with rich grain boundaries for lithium ion batteries. Journal of Power Sources, 2014, 266:114-120. DOI URL
[11]	LU X, ZHAO L, HE X Q, et al. Lithium storage in Li₄Ti₅O₁₂ spinel: the full static picture from electron microscopy. Advanced Materials, 2012, 24(24):3233-3238. DOI URL
[12]	TAN G Q, WU F, LI L, et al. Coralline glassy lithium phosphate- coated LiFePO₄ cathodes with improved power capability for lithium ion batteries. Journal of Physical Chemistry C, 2013, 117(12):6013-6021. DOI URL
[13]	LEE S W, KIM M S, JEONG J H, et al. Li₃PO₄ surface coating on Ni-rich LiNi_0.6Co_0.2Mn_0.2O₂ by a citric acid assisted Sol-Gel method: improved thermal stability and high-voltage performance. Journal of Power Sources, 2017, 360:206-214. DOI URL
[14]	HIRAYAMA M, KIM K, TOUJIGAMORI T, et al. Epitaxial growth and electrochemical properties of Li₄Ti₅O₁₂ thin-film lithium battery anodes. Dalton Transactions, 2011, 40(12):2882-2887. DOI URL
[15]	ZHAO L, HU Y S, LI H, et al. Porous Li₄Ti₅O₁₂ coated with N-doped carbon from ionic liquids for Li-ion batteries. Advanced Materials, 2011, 23(11):1385-1388. DOI URL
[16]	HALL D S, GAUTHIER R, ELDESOKY A, et al. New chemical insights into the beneficial role of Al₂O₃ cathode coatings in lithium-ion cells. ACS Applied Materials & Interfaces, 2019, 11(15):14095-14100.
[17]	BORGHOLS W J H, WAGEMAKER M, LAFONT U, et al. Size effects in the Li₄+_xTi₅O₁₂ spinel. Journal of the American Chemical Society, 2009, 131(49):17786-17792. DOI URL
[18]	GANAPATHY S, WAGEMAKER M J A N. Nanosize storage properties in spinel Li₄Ti₅O₁₂ explained by anisotropic surface lithium insertion. ACS Nano, 2012, 6(10):8702-8712. DOI URL
[19]	WAGEMAKER M, SIMON D R, KELDER E M, et al. A kinetic two-phase and equilibrium solid solution in spinel Li₄+_xTi₅O₁₂. Advanced Materials, 2010, 18(23):3169-3173. DOI URL
[20]	JUNG Y S, LU P, CAVANAGH A S, et al. Unexpected improved performance of ALD coated LiCoO₂/graphite Li-ion batteries. Advanced Energy Materials, 2013, 3(2):213-219. DOI URL
[21]	MOGUSMILANKOVIC A, SANTIC A, KARABULUT M, et al. Study of electrical properties of MoO₃-Fe₂O₃-P₂O₅ and SrO-Fe₂O₃-P₂O₅ glasses by impedance spectroscopy. II. Journal of Non-Crystalline Solids, 2003, 330(1/2/3):128-141. DOI URL
[22]	AHN D, XIAO X J E C. Extended lithium titanate cycling potential window with near zero capacity loss. Electrochemistry Communications, 2011, 13(8):796-799. DOI URL
[23]	GE H, LI N, LI D Y, et al. Study on the theoretical capacity of spinel lithium titanate induced by low-potential intercalation. Journal of Physical Chemistry C, 2009, 113(16):6324-6326. DOI URL
[24]	LEVI M D, SALITRA G, MARKOVSKY B, et al. Solid-state electrochemical kinetics of Li-ion intercalation into Li₁-_xCoO₂: simultaneous application of electroanalytical techniques SSCV, PITT, and EIS. Journal of The Electrochemical Society, 1999, 146(4):1279-1289. DOI URL

非晶态磷酸锂包覆钛酸锂电极在0.01~3.00 V电压范围的性能研究

Performance of Amorphous Lithium Phosphate Coated Lithium Titanate Electrodes in Extended Working Range of 0.01-3.00 V

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