锂离子电池负极材料钛酸锂的研究进展

doi:10.15541/jim20170330

摘要/Abstract

摘要：

锂离子电池作为一种动力能源, 在电动汽车和各种储能系统中有着良好的应用前景。尖晶石结构的钛酸锂(Li₄Ti₅O₁₂)负极材料具有较高的脱嵌锂电位平台、优异的循环稳定性、以及突出的安全性能, 被认为是一种非常有潜力的锂离子电池负极材料, 在锂离子动力电池中具有巨大的发展潜力。然而, 尖晶石型Li₄Ti₅O₁₂存在着本征导电率低, 理论容量小等缺陷, 极大地限制了其规模化应用, 需要进一步改善和提高。本文总结了尖晶石型Li₄Ti₅O₁₂材料在结构形貌、制备方法和性能方面的研究进展, 深入分析和讨论了离子掺杂、碳表面改性和纳米化等改性方法对尖晶石型Li₄Ti₅O₁₂综合电化学性能的改善效果, 并展望了尖晶石型Li₄Ti₅O₁₂作为锂离子电池负极材料未来的发展方向。

关键词: 钛酸锂, 负极材料, 锂离子电池

Abstract:

With the increasing demand for light, small, high power rechargeable lithium ion batteries in the application of mobile phones, laptop computers, electric vehicles, hybrid electric vehicles, electrochemical energy storage, and smart grids, the development of anode materials with high safety, environmental benignity, high power density, and long cycle life is in progress in recent years. The spinel lithium titanium oxide (Li₄Ti₅O₁₂) anode has become more attractive as alternative anode because of its high safety, abundant titanium dioxide raw materials, stable charge/discharge voltage plateau of 1.5 V (vs. Li/Li⁺), and excellent cycling performance due to its zero-strain volume during charge/discharge process. However, the commercial use of Li₄Ti₅O₁₂ anode material has been hindered by the low intrinsic electronic conductivity. This review focuses on recent studies of the electronic structure and performance, synthesis methods and strategies for improvement in the lithium storage capacity, charge/discharge characteristics, then on its near future development.

Key words: Li₄Ti₅O₁₂, anode materials, lithium-ion batteries

中图分类号:

TM912

谭毅, 薛冰. 锂离子电池负极材料钛酸锂的研究进展[J]. 无机材料学报, 2018, 33(5): 475-482.

TAN Yi, XUE Bing. Research Progress on Lithium Titanate as Anode Material in Lithium-ion Battery[J]. Journal of Inorganic Materials, 2018, 33(5): 475-482.

图/表 10

参考文献 60

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Ion	Radius /nm	Doping content molar ratio	Size/nm	Initial discharge capacity/(mAh^.g^-1)	Cycle performance/ (mAh^.g^-1)	Method	Ref.
Cation doping in the Li sites(radius 0.076 nm)
Mg²⁺	0.0720	0.20	100-200	190.0(1C)^a	179.0(1C, 100)^b; 150.0(5C, 100)	Solid state reaction	[30]
Ca²⁺	0.1000	0.10	1000-2000	169.7(0.5C)	162.4(1C, 100); 148.8(5C, 100)	Solid state reaction	[31]
Sc³⁺	0.0745	0.05	200	174.0(1C); 94.0(40C)	94.0(40C, 50)	Sol-Gel	[32]
Cu²⁺	0.0730	0.05	200-600	158.0(0.1C)	143.8(0.1C, 150)	Sol-Gel	[33]
La³⁺	0.1032	0.06	24.5	169.0(0.1C)	153.4(1C, 10); 146.9(5C, 10)	Liquid method	[34]
Cation doping in the Ti sites (radiusTi³⁺0.067 nm, Ti⁴⁺0.0605 nm)
Al³⁺	0.0535	0.15	50-200	216.0(1C); 163.0(10C)	180.0(5C, 50); 160.0(10C, 50)	Cellulose-assisted glycine-nitratecombustion	[35]
Zr⁴⁺	0.0720	0.03	200	165.0(5C); 152.0(10C)	142.0(5C, 200); 127.0(10C, 200)	Liquid method	[36]
Ce⁴⁺	0.0870	0.10	<1000	190.0(0.2C); 40.0(2C)	140.0(2C, 100)	Solid state reaction	[37]
Ta⁵⁺	0.0640	0.05	500-1000	193.0(0.2C)	132.0(5C, 100)	Solid state reaction	[38]
Anions doping in the O site (radius 0.14 nm)
Cl^-	0.181	0.2	3-8 μm	148.7(0.5C)	133.8(0.5C, 50)	Solid state reaction	[39]
Cl^-	0.181	0.2	3-8 μm	120.7(2C)	133.8(0.5C, 50)	Solid state reaction	[39]
Br^-	0.196	0.3	1-2 μm	174.0(0.2C)	138.0(10C, 100); 104.0(210C,100)	Solid state reaction	[40]

Ion	Radius /nm	Doping content molar ratio	Size/nm	Initial discharge capacity/(mAh^.g^-1)	Cycle performance/ (mAh^.g^-1)	Method	Ref.
Cation doping in the Li sites(radius 0.076 nm)
Mg²⁺	0.0720	0.20	100-200	190.0(1C)^a	179.0(1C, 100)^b; 150.0(5C, 100)	Solid state reaction	[30]
Ca²⁺	0.1000	0.10	1000-2000	169.7(0.5C)	162.4(1C, 100); 148.8(5C, 100)	Solid state reaction	[31]
Sc³⁺	0.0745	0.05	200	174.0(1C); 94.0(40C)	94.0(40C, 50)	Sol-Gel	[32]
Cu²⁺	0.0730	0.05	200-600	158.0(0.1C)	143.8(0.1C, 150)	Sol-Gel	[33]
La³⁺	0.1032	0.06	24.5	169.0(0.1C)	153.4(1C, 10); 146.9(5C, 10)	Liquid method	[34]
Cation doping in the Ti sites (radiusTi³⁺0.067 nm, Ti⁴⁺0.0605 nm)
Al³⁺	0.0535	0.15	50-200	216.0(1C); 163.0(10C)	180.0(5C, 50); 160.0(10C, 50)	Cellulose-assisted glycine-nitratecombustion	[35]
Zr⁴⁺	0.0720	0.03	200	165.0(5C); 152.0(10C)	142.0(5C, 200); 127.0(10C, 200)	Liquid method	[36]
Ce⁴⁺	0.0870	0.10	<1000	190.0(0.2C); 40.0(2C)	140.0(2C, 100)	Solid state reaction	[37]
Ta⁵⁺	0.0640	0.05	500-1000	193.0(0.2C)	132.0(5C, 100)	Solid state reaction	[38]
Anions doping in the O site (radius 0.14 nm)
Cl^-	0.181	0.2	3-8 μm	148.7(0.5C)	133.8(0.5C, 50)	Solid state reaction	[39]
Cl^-	0.181	0.2	3-8 μm	120.7(2C)	133.8(0.5C, 50)	Solid state reaction	[39]
Br^-	0.196	0.3	1-2 μm	174.0(0.2C)	138.0(10C, 100); 104.0(210C,100)	Solid state reaction	[40]

Ion	Radius/nm	Doping content molar ratio	Size/ nm	Initial discharge capacity/(mAh^.g^-1)	Cycle performance/ (mAh^.g^-1)	Method	Ref.
Zn²⁺	0.074	0.20	1000-2000	(0-2.5 V)	216.4(0.5C, 30)	Solid state reaction	[6]
				271.6(0.5C)^a; 223.0(3C);	198.0(3C, 100)
				271.6(0.5C)^a; 223.0(3C);	186.0(5C, 200)
				206.0(5C)
Nb⁵⁺	0.064	0.05		(0-2.5 V)	231.0(0.12C, 100)	Sol-Gel	[46]
Nb⁵⁺	0.064	0.05		351.0(0.12C)		Sol-Gel	[46]
Ru⁴⁺	0.062	0.05	100-200	(0.01-2.5 V)	259.0(3C, 100); 131.0(60C, 100)	Reverse microemulsion method	[47]
Ru⁴⁺	0.062	0.05	100-200	274.0(3C)	259.0(3C, 100); 131.0(60C, 100)	Reverse microemulsion method	[47]
Bi⁺³⁺	0.103	0.10	500-1000	(0.01-2.5 V)	203.0(1C, 50)	Solid state reaction	[48]
Bi⁺³⁺	0.103	0.10	500-1000	214.0(1C)		Solid state reaction	[48]

Ion	Radius/nm	Doping content molar ratio	Size/ nm	Initial discharge capacity/(mAh^.g^-1)	Cycle performance/ (mAh^.g^-1)	Method	Ref.
Zn²⁺	0.074	0.20	1000-2000	(0-2.5 V)	216.4(0.5C, 30)	Solid state reaction	[6]
				271.6(0.5C)^a; 223.0(3C);	198.0(3C, 100)
				271.6(0.5C)^a; 223.0(3C);	186.0(5C, 200)
				206.0(5C)
Nb⁵⁺	0.064	0.05		(0-2.5 V)	231.0(0.12C, 100)	Sol-Gel	[46]
Nb⁵⁺	0.064	0.05		351.0(0.12C)		Sol-Gel	[46]
Ru⁴⁺	0.062	0.05	100-200	(0.01-2.5 V)	259.0(3C, 100); 131.0(60C, 100)	Reverse microemulsion method	[47]
Ru⁴⁺	0.062	0.05	100-200	274.0(3C)	259.0(3C, 100); 131.0(60C, 100)	Reverse microemulsion method	[47]
Bi⁺³⁺	0.103	0.10	500-1000	(0.01-2.5 V)	203.0(1C, 50)	Solid state reaction	[48]
Bi⁺³⁺	0.103	0.10	500-1000	214.0(1C)		Solid state reaction	[48]

Carbon source	Carbon content/wt%	Thickness/ nm	Initial discharge capacity/(mAh^.g^-1)	Cycle performance/ (mAh^.g^-1)	Method	Ref.
LPAN+CB	3.64	3-5	166.2(10C)	141.9(10C, 200)	Solid state reaction	[49]
PEDOT	10.00	10	168.7(1C)	167.9(1C, 100)	Hydrothermal reaction	[50]
Sucrose	8.60	2-4	156.7(40C); 142.1(60C); 132.8(80C)	114.2(40C, 200); 98.1(60C, 200) 82.7(80C, 200)	One-step liquid process	[51]
Citric acid	1.32	2-3	165.7(1C); 161.7(5C); 153.9(10C); 147.9(20C)	144.9(20C, 50)	Sol-Gel	[52]
Glucose	8.96	8	170.9(0.5C)	155.6(1C, 100)	Hydrothermal-solid state reaction	[53]