Y3+掺杂Li4Ti5O12负极材料的电荷输运特性及电化学性能研究

doi:10.11868/j.issn.1001-4381.2021.000209

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摘要

以Li₂CO₃与锐钛矿型TiO₂为原料，六水合硝酸钇（Y（NO₃）₃·6H₂O）为钇源，采用球磨辅助固相法合成了Li₄Ti_5-xY_xO₁₂（x=0，0.05，0.10，0.15，0.20）负极材料。通过X射线衍射分析（XRD）、扫描电镜（SEM）、能谱仪（EDS）与X射线光电子能谱（XPS）分别对材料的物相与形貌进行表征分析，并利用电化学工作站对材料的电化学性能与电荷输运特性进行测试。结果表明，Y³⁺掺杂没有影响尖晶石型Li₄Ti₅O₁₂（LTO）材料的尖晶石结构，x=0.15时，Li₄Ti_4.85Y_0.15O₁₂样品的离子与电子电导率分别为2.68×10^-7 S·cm^-1和1.49×10^-9 S·cm^-1，比本征材料提升了1个数量级，表现出良好的电荷输运特性。电化学测试表明，Li₄Ti_4.85Y_0.15O₁₂样品在0.1 C倍率首次放电比容量可达171 mAh·g^-1，且在10 C与20 C高倍率下仍然拥有102 mAh·g^-1和79 mAh·g^-1的较高比容量，循环200周次后容量保持率分别为92.6%和89.1%，表现出良好的倍率特性。

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	吴冰
	刘磊
	王献志
	肖潇
	杨豹
	赵锦涛
	古成前
	马雷

关键词 ：掺杂, 钛酸锂, 电导率, 稀土离子, 高倍率

Abstract：

Li₄Ti_5-xY_xO₁₂ (x=0, 0.05, 0.10, 0.15, 0.20) anode materials were synthesized by ball milling assisted solid-state method used Li₂CO₃ and anatase TiO₂ as raw materials and yttrium nitrate (Y(NO₃)₃·6H₂O) as yttrium source. The phase and morphology of the materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), respectively. The electrochemical performance and transport characteristics of the materials were tested and analyzed by an electrochemical workstation. The results show that there is no effect of Y³⁺ doping on the spinel structure of LTO material. When x=0.15, the ion and electronic conductivities of the Li₄Ti_4.85Y_0.15O₁₂ sample are 2.68×10^-7 S·cm^-1 and 1.49×10^-9 S·cm^-1, respectively, which are an order of magnitude higher than that of the intrinsic LTO, and present good transport characteristics. Electrochemical tests show that a first discharge capacity of Li₄Ti_4.85Y_0.15O₁₂ sample can reach 171 mAh·g^-1 at 0.1 C rate. The sample still has a higher specific capacity of 102 mAh·g^-1 and 79 mAh·g^-1 at a high rate of 10 C and 20 C, respectively.After 200 cycles, the capacity retention rates are 92.6% and 89.1% respectively, showing good magnification characteristics.

Key words： doping lithium titanate conductivity rare earth ion high rate

收稿日期: 2021-03-10 出版日期: 2022-10-24

中图分类号:

TM912.9

基金资助:天津市重点研究开发项目(19YFHBQY00030);河北省自然科学基金(F2021201007);河北省自然科学基金(B202101051)

通讯作者: 刘磊 E-mail: beimingzy@126.com

作者简介: 刘磊(1979—), 男, 副教授, 博士, 研究方向为离子电池及其正、负极材料, 联系地址: 河北省保定市七一东路2666号河北大学电信学院(071002), E-mail: beimingzy@126.com

引用本文:

吴冰, 刘磊, 王献志, 肖潇, 杨豹, 赵锦涛, 古成前, 马雷. Y³⁺掺杂Li₄Ti₅O₁₂负极材料的电荷输运特性及电化学性能研究[J]. 材料工程, 2022, 50(10): 102-110.
Bing WU, Lei LIU, Xianzhi WANG, Xiao XIAO, Bao YANG, Jintao ZHAO, Chengqian GU, Lei MA. Transport characteristics and electrochemical properties of Y³⁺ doped Li₄Ti₅O₁₂ as anode material. Journal of Materials Engineering, 2022, 50(10): 102-110.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2021.000209 或 http://jme.biam.ac.cn/CN/Y2022/V50/I10/102

Fig.1 Li₄Ti_5-xY_xO₁₂(x=0，0.05，0.10，0.15，0.20)样品的XRD图谱，插图为样品(111)峰局部放大图谱

Table 1 Li₄Ti_5-xY_xO₁₂(x=0，0.05，0.10，0.15，0.20)样品的晶格参数

Fig.2 Li₄Ti_4.85Y_0.15O₁₂样品在不同煅烧温度下的XRD谱图

Fig.3 Li₄Ti_4.85Y_0.15O₁₂样品在不同煅烧温度下的SEM图

Fig.4 Li₄Ti₅O₁₂与Li₄Ti_4.85Y_0.15O₁₂样品的XPS光谱图
(a)总谱图; (b)Li1s;(c)O1s;(d)Ti2p;(e)Y3d

Fig.5 Li₄Ti_5-xY_xO₁₂(x=0，0.05，0.10，0.15，0.20)样品的电荷输运特性变化
(a)交流阻抗; (b)J-V曲线

Table 2 Li₄Ti_5-xY_xO₁₂(x=0，0.05，0.1，0.15，0.2)的电荷输运特性参数

Fig.6 Li₄Ti_4.85Y_0.15O₁₂样品不同温度下电荷输运特性变化
(a)不同温度下的交流阻抗图谱, 插图为Arrhenius图; (b)离子电导率随温度变化的曲线图

Fig.7 Li₄Ti_5-xY_xO₁₂(x=0，0.05，0.10，0.15，0.20)样品的充放电性能
(a)0.1 C下首次充放电曲线；(b)0.1 C下50周次循环性能; (c)倍率性能; (d)Li₄Ti₅O₁₂与Li₄Ti_4.85Y_0.15O₁₂样品在10，20 C高倍率下的性能比较

Table 3 LTO负极材料的电化学性能

1	PROSINI P P , MANCINI R , PETRUCCI L , et al. Li₄Ti₅O₁₂as anode in all-solid-state, plastic, lithium-ion batteries for low-power applications[J]. Solid State Ionics, 2001, 144 (1/2): 185- 192.
2	HU X , LIN Z , YANG K , et al. Influence factors on electrochemical properties of Li₄Ti₅O₁₂/C anode material pyrolyzed from lithium polyacrylate[J]. Journal of Alloys and Compounds, 2010, 506 (1): 160- 166. doi: 10.1016/j.jallcom.2010.06.165
3	RONCI F , REALE P , SCROSATI B , et al. High-resolution in-situ structural measurements of the Li₄Ti₅O₁₂"zero-strain" insertion material[J]. The Journal of Physical Chemistry B, 2002, 106 (12): 3082- 3086. doi: 10.1021/jp013240p
4	OHZUKU T , UEDA A , YAMAMOTO N , et al. Factor affecting the capacity retention of lithium-ion cells[J]. Journal of Power Sources, 1995, 54 (1): 99- 102. doi: 10.1016/0378-7753(94)02047-7
5	DONG H Y , HE Y B , LI B H , et al. Controlled preparation and electrochemical performance of a flaky Li₄Ti₅O₁₂-graphene hybrid with a high crystallinity[J]. New Carbon Materials, 2016, 31 (2): 115- 120.
6	LI J , TANG Z , ZHANG Z , et al. H-titanate nanotube: a novel lithium intercalation host with large capacity and high rate capability[J]. Electrochemistry Communications, 2005, 7 (1): 62- 67. doi: 10.1016/j.elecom.2004.11.009
7	JUNG H G , MYUNG S T , CHONG S Y , et al. Microscale spherical carbon-coated Li₄Ti₅O₁₂as ultra high power anode material for lithium batteries[J]. Energy Environmental Science, 2011, 4 (4): 1345- 1351. doi: 10.1039/c0ee00620c
8	WANG W , JIANG B , XIONG W , et al. A nanoparticle Mg-doped Li₄Ti₅O₁₂ for high rate lithium-ion batteries[J]. Electrochimica Acta, 2013, 114, 198- 204. doi: 10.1016/j.electacta.2013.10.035
9	HAN Y R , DUH J G . Synthesis of entanglement structure in nanosized Li₄Ti₅O₁₂/multi-walled carbon nanotubes composite anode material for Li-ion batteries by ball-milling-assisted solid-state reaction[J]. Journal of Power Sources, 2012, 198, 294- 297. doi: 10.1016/j.jpowsour.2011.09.063
10	CHATURVEDI P , KANAGARAJ A B , AL NAHYAN M S , et al. Electrical and electrochemical properties of carbon nanotube-based free standing LTO electrodes for current collector-free Li-ion batteries[J]. Current Applied Physics, 2019, 19 (11): 1150- 1155. doi: 10.1016/j.cap.2019.07.009
11	KIM G O , HONG J E , RYU K S . Enhancement of high rate performance and diffusion properties for Li₄Ti₅O₁₂anode materials by carbon additive[J]. Materials Research Innovations, 2014, 19 (4): 244- 250.
12	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. doi: 10.3969/j.issn.1673-1433.2021.03.017
12	LIAN T R , LU Y X , WU B , et al. Preparation and transport properties of nano-Li₄Ti₅O₁₂ anode materials[J]. Journal of Materials Engineering, 2021, 49 (3): 59- 66. doi: 10.3969/j.issn.1673-1433.2021.03.017
13	LI Q , BING X , YI T , et al. The Mg/Zr codoping on morphology and electrochemical properties of Li₄Ti₅O₁₂ anode materials[J]. Chemical Physics Letters, 2018, 711, 15- 22. doi: 10.1016/j.cplett.2018.09.012
14	QI Y , HUANG Y , JIA D , et al. Preparation and characterization of novel spinel Li₄Ti₅O_12-XBr_X anode materials[J]. Electrochimica Acta, 2009, 54 (21): 4772- 4776. doi: 10.1016/j.electacta.2009.04.010
15	WOLFENSTINE J , LEE U , ALLEN J L . Electrical conductivity and rate-capability of Li₄Ti₅O₁₂as a function of heat-treatment atmosphere[J]. Journal of Power Sources, 2009, 54 (21): 4772- 4776.
16	YI T F , SHU J , ZHU Y R , et al. High-performance Li₄Ti_5-xV_xO₁₂(0≤x≤0.3) as an anode material for secondary lithium-ion battery[J]. Electrochimica Acta, 2009, 54 (28): 7464- 7470. doi: 10.1016/j.electacta.2009.07.082
17	SHA H W , YIN W Z , JIAN Z X , et al. Effects of dopant on the electrochemical performance of Li₄Ti₅O₁₂ as electrode material for lithium ion batteries[J]. Journal of Power Sources, 2007, 165 (1): 408- 412. doi: 10.1016/j.jpowsour.2006.12.010
18	BAI Y J , GONG C , QI Y X , et al. Excellent long-term cycling stability of La-doped Li₄Ti₅O₁₂ anode material at high current rates[J]. Journal of Materials Chemistry, 2012, 22 (36): 19054- 19060. doi: 10.1039/c2jm34523d
19	ZHANG Q , LI X , MENG Y S , et al. Structural and electrochemical properties of Gd-doped Li₄Ti₅O₁₂ as anode material with improved rate capability for lithium-ion batteries[J]. Journal of Power Sources, 2015, 280, 355- 362. doi: 10.1016/j.jpowsour.2015.01.124
20	JI M , XU Y , ZHAO Z , et al. Preparation and electrochemical performance of La³⁺ and F^- co-doped Li₄Ti₅O₁₂anode material for lithium-ion batteries[J]. Journal of Power Sources, 2014, 263, 296- 303. doi: 10.1016/j.jpowsour.2014.04.051
21	XU H , WANG S , WILSON H , et al. Y-doped NASICON-type LiZr₂(PO₄)₃solid electrolytes for lithium-metal batteries[J]. ChemMater, 2017, 12 (26): 131- 136.
22	LI F T , WANG Q , RAN J , et al. Ionic liquid self-combustion synthesis of BiOBr/Bi₂₄O₃₁Br₁₀ heterojunctions with exceptional visible-light photocatalytic performances[J]. Nanoscale, 2014, 7 (3): 16- 26.
23	WANG Y Z , YANG H , XUE X X . Synergistic antibacterial activity of TiO₂ co-doped with zinc and yttrium[J]. Vacuum, 2014, 107, 28- 32. doi: 10.1016/j.vacuum.2014.03.026
24	SUN Z , LIU L , LU Y , et al. Preparation and ionic conduction of Li_1.5Al_0.5Ge_1.5(PO₄)₃ solid electrolyte using inorganic germanium as precursor[J]. Journal of the European Ceramic Society, 2019, 39, 402- 408. doi: 10.1016/j.jeurceramsoc.2018.09.025
25	LIU L , WANG P , LI J , et al. Hydrothermal preparation and intrinsic transport properties of nanoscale Li₂FeSiO₄[J]. Solid State Ionics, 2018, 320, 353- 359. doi: 10.1016/j.ssi.2018.03.025
26	VIKRAM B B , VIJAYA B K , TEWODROS A G , et al. Structural and electrical properties of Li₄Ti₅O₁₂ anode material for lithium-ion batteries[J]. Results in Physics, 2018, 9, 284- 289. doi: 10.1016/j.rinp.2018.02.050
27	ALI B , MUHAMMAD R , ANANG D A , et al. Ge-doped Li₄Ti₅Ge_xO₁₂(x=0.05) as a fast-charging, long-life bi-functional anode material for lithium- and sodium-ion batteries[J]. Ceramics International, 2020, 46 (10): 16556- 16563. doi: 10.1016/j.ceramint.2020.03.223
28	TSAI P C , NASARA R N , SHEN Y C , et al. Ab initio phase stability and electronic conductivity of the doped-Li₄Ti₅O₁₂ anode for Li-ion batteries[J]. Acta Materialia, 2019, 175, 196- 205. doi: 10.1016/j.actamat.2019.06.014
29	ZHANG Q , CHEN J . Preparation and performance of hollow spherical Li₄Ti₅O₁₂doped by Mg²⁺[J]. Journal of Wuhan University of Technology-Mater Sci Ed, 2020, 35 (1): 107- 112. doi: 10.1007/s11595-020-2233-5
30	CHEN C , LIU X , AI C , et al. Enhanced lithium storage capability of Li₄Ti₅O₁₂anode material with low content Ce modification[J]. Journal of Alloys and Compounds, 2017, 714, 71- 78. doi: 10.1016/j.jallcom.2017.04.184

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