Research Progress on Lithium Titanate as Anode Material in Lithium-ion Battery

doi:10.15541/jim20170330

Abstract

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

CLC Number:

TM912

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.

Figures/Tables 10

References 60

[1]	LI Z Y, DING F X, ZHAO Y G,et al. Synthesis and electrochemical performance of Li4Ti5O12 submicrospheres coated with TiN as anode materials for lithium-ion battery. Ceram. Int., 2016, 42(14): 15464-15470.
[2]	HUI Y N, CAO L Y, XU Z W,et al. In situ synthesis of core-shell Li4Ti5O12@polyaniline composites with enhanced rate performance for lithium-ion battery anodes. J. Mater. Sci. Techno., 2016, 33(3): 231-238.
[3]	CHEN S, XIN Y L, ZHOU Y Y,et al. Self-supported Li4Ti5O12 nanosheet arrays for lithium ion batteries with excellent rate capability and ultralong cycle life. Energy Environ. Sci., 2014, 7(6): 1924-1930.
[4]	YI T F, YANG S Y, XIE Y.Recent advances of Li4Ti5O12 as a promising next generation anode material for high power lithium- ion batteries.J. Mater. Chem. A, 2015, 3(11): 5750-5777.
[5]	BORGHOLS W J H, WAGEMAKER M, LAFONT U,et al. Size effects in the Li4+xTi5O12 spinel. J. Am. Chem. Soc., 2009, 131(49): 17786-17792.
[6]	YI T F, LIU H P, ZHU Y R,et al. Improving the high rate performance of Li4Ti5O12 through divalent zinc substitution. J. Power Sources, 2012, 215: 258-265.
[7]	WIKENING M, IWANIAK W, HEINE J,et al. Microscopic Li self-diffusion parameters in the lithiated anode material Li4+xTi5O12(0 < or = x < or = 3) measured by 7Li solid state NMR. Phys. Chem. Chem. Phys., 2007, 9(47): 6199-6202.
[8]	YANG S, WANG Q F, LU M W, et al. Synthesis of graphitized carbon, nanodiamond and graphene supported Li4Ti5O12 and comparison of their electrochemical performance as anodes for lithium ion batteries. Appl. Surf. Sci., 2016, 389: 428-437.
[9]	ZHU G N, WANG Y G, XIA Y Y.Ti-based compounds as anode materials for Li-ion batteries.Energy Environ. Sci., 2012, 5(5): 6652-6667.
[10]	Yang L Y, LI H Z, LIU J,et al. Effects of TiO2 phase on the performance of Li4Ti5O12 anode for lithium-ion batteries. J. Alloys Compd., 2016, 689: 812-819.
[11]	MA J, WANG C, WROBLEWSKI S.Kinetic characteristics of mixed conductive electrodes for lithium ion batteries.J. Power Sources, 2007, 164(2): 849-856.
[12]	TAKAMI N, HOSHINA K, INAGAKI H.Lithium diffusion in Li4/3Ti5/3O4 particles during insertion and extraction.J. Electrochem. Soc., 2011, 158(6): A725-A730.
[13]	LIU W, ZHANG J, WANG Q,et al. The effects of Li2CO3 particle size on the properties of lithium titanate as anode material for lithium-ion batteries. Ionics, 2014, 20(11): 1553-1560.
[14]	CHEN C, SPEARS M, WONDRE F, et al. Crystal growth and superconductivity of LiTi2O4 and Li1+1/3Ti2-1/3O4.J. Cryst. Growth, 2003, 250(1/2): 139-145.
[15]	GUERFI A, SEVIGNY S, LAGACE M,et al. Nano-particle Li4Ti5O12 spinel as electrode for electrochemical generators. J. Power Sources, 2003, 119(121): 88-94.
[16]	MICHALSKA M, KRAJEWSKI M, ZIOLKOWSKA D,et al. Influence of milling time in solid-state synthesis on structure, morphology and electrochemical properties of Li4Ti5O12 of spinel structure. Powder Technol., 2014, 266(6): 372-377.
[17]	SENNA M, FAVIAN M, KAVAN L,et al. Electrochemical properties of spinel Li4Ti5O12 nanoparticles prepared via a low-temperature solid route. J. Solid State Electrochem., 2016, 20(10): 2673-2683.
[18]	HAN S W, JEONG J, YOON D H.Effects of high-energy milling on the solid-state synthesis of pure nano-sized Li4Ti5O12 for high power lithium battery applications.Appl. Phys. A, 2014, 114(3): 925-930.
[19]	WANG Y Q, ZHAO J, QU J,et al. Investigation into the surface chemistry of Li4Ti5O12 nanoparticles for lithium ion batteries. Appl. Mater. Interfaces, 2016, 8(39): 26008-26012.
[20]	QIU C X, YUAN Z Z, LIU L,et al. Sol-Gel preparation and electrochemical properties of La-doped Li4Ti5O12 anode material for lithium-ion battery. J. Solid State Electrochem., 2013, 17(3): 841-847.
[21]	MOHAMMADI M R, FRAY D J.Low temperature nanostructured lithium titanates: controlling the phase composition, crystal structure and surface area.J. Sol-Gel Sci. Techn., 2010, 55(1): 19-35.
[22]	LIU G Y, ZHANG R X, BAO K Y,et al. Synthesis of nano- Li4Ti5O12 anode material for lithium ion batteries by a biphasic interfacial reaction route. Ceram. Int., 2016, 42(9): 11468-11472.
[23]	ZHU K X, GAO H Y, HU G X,et al. Scalable synthesis of hierarchical hollow Li4Ti5O12 microspheres assembled by zigzag-like nanosheets for high rate lithium-ion batteries. J. Power Sources, 2017, 340: 263-272.
[24]	GUO Q J, LI S Y, WANG H,et al. Molten salt synthesis of nano-sized Li4Ti5O12 doped with Fe2O3 for use as anode material in the lithium ion battery. RSC Adv., 2014. 4(104): 60327-60333.
[25]	ZHAO Y G, LI J L, LI Z Y,et al. Pr-modified Li4Ti5O12 nanofibers as an anode material for lithium-ion batteries with outstanding cycling performance and rate performance. Ionics, 2017. 23(3): 597-605.
[26]	YANG L H, DONG C D, GUO J.Hybrid microwave synthesis and characterization of the compounds in the Li-Ti-O system.J. Power Sources, 2008, 175(1): 575-580.
[27]	LI J, JIN Y L, ZHANG X G,et al. Microwave solid-state synthesis of spinel Li4Ti5O12 nanocrystallites as anode material for lithium- ion batteries. Solid State Ionics, 2007, 178(29/30): 1590-1594.
[28]	JIA X L, KAN Y F, ZHU X,et al. Building flexible Li4Ti5O12/CNT lithium-ion battery anodes with superior rate performance and ultralong cycling stability. Nano Energy, 2014, 10: 344-352.
[29]	WOLFENSTINE J, ALLEN J L.Electrical conductivity and charge compensation in Ta doped Li4Ti5O12.J. Power Sources, 2008, 180(1): 582-585.
[30]	LI F Y, ZHENG M, LI J,et al. Preparation and electrochemical performance of Mg-doped Li4Ti5O12 nanoparticles as anode materials for lithium-ion batteries. Int. J. Electrochem. Sci., 2015, 10(12): 10445-10453.
[31]	ZHANG Q Y, ZHANG C L, LI B,et al. Preparation and electrochemical properties of Ca-doped Li4Ti5O12 as anode materials in lithium-ion battery materials for flexible Li-ion batteries. Electrochim. Acta, 2013, 98(16): 146-152.
[32]	ZHANG Y Y, ZHANG C M, LIN Y,et al. Influence of Sc3+ doping in B-site on electrochemical performance of Li4Ti5O12 anode materials for lithium-ion battery. J. Power Sources, 2014, 250(3): 50-57.
[33]	GE Y Q, JIANG H, FU K,et al. Copper-doped Li4Ti5O12/carbon nanofiber composites as anode for high-performance sodium-ion batteries. J. Power Sources, 2014, 272: 860-865.
[34]	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. Mater. Chem., 2012, 22(36): 19054-19060.
[35]	CAI R, JIANG S M, YU X,et al. A novel method to enhance rate performance of an Al-doped Li4Ti5O12 electrode by post-synthesis treatment in liquid formaldehyde at room temperature. J. Mater. Chem., 2012, 22(16): 8013-8021.
[36]	CHEN Y J, MU D B, HANG R,et al. The Improvement of Discharge Capacity of Zr-doped Lithium Titanate for Lithium Ion Batteries. Matec Web Conf., 2016, 67: 06028.
[37]	ZHOU T P, FENG X Y, GUO X,et al. Solid-state synthesis and electrochemical performance of Ce-doped Li4Ti5O12 anode materials for lithium-ion batteries. Electrochim. Acta, 2015, 174: 369-375.
[38]	GUO M, WANG S Q, DING L X,et al. Tantalum-doped lithium titanate with enhanced performance for lithium-ion batteries. J. Power Sources, 2015, 283(25): 372-380.
[39]	HUANG Y D, QI Y L, JIA D Z,et al. Synthesis and electrochemical properties of spinel Li4Ti5O12-xClx anode materials for lithium- ion batteries. J. Solid State Electrochem., 2012, 16(5): 2011-2016.
[40]	WANG J Q, YANG Z Z, LI W H,et al. Nitridation Br-doped Li4Ti5O12 anode for high rate lithium ion batteries. J. Power Sources, 2014, 266(1): 323-331.
[41]	DING K Q, ZHAO J, SUN Y Z,et al. Using potassium ferricyanide as a dopant to prepare K and Fe co-doped Li4Ti5O12. Ceram. Int., 2016, 42(16): 19187-19194.
[42]	BAI X, LI W, WEI A J,et al. Preparation and electrochemical properties of Mg2+ and F- co-doped Li4Ti5O12 anode material for use in the lithium-ion batteries materials for flexible Li-ion batteries. Electrochim. Acta, 2016, 222: 1045-1055.
[43]	XU P, HUANG X B, REN Y R,et al. Na+ and Zr4+ co-doped Li4Ti5O12 as anode materials with superior electrochemical performance for lithium ion batteries. RSC Adv., 2016, 6(93): 90455-90461.
[44]	LONG W M, WANG X Y, YANG S Y,et al. Electrochemical properties of Li4Ti5-2xNixMnxO12 compounds synthesized by Sol-Gel process. Mater. Chem. Phys., 2011, 131(1): 431-435.
[45]	SHKROB I A, ZHU Y, MARIN T W,et al. Reduction of carbonate electrolytes and the formation of solid-electrolyte interface (SEI) in lithium-ion batteries. 1. spectroscopic observations of radical intermediates generated in one-electron reduction of carbonates. J. Phys. Chem. C, 2013, 117(38): 19255-19269.
[46]	TIAN B B, XIANG H F, ZHANG L,et al. Effect of Nb-doping on electrochemical stability of Li4Ti5O12 discharged to 0 V. J. Solid State Electrochem., 2012, 16(1): 205-211.
[47]	WANG W, WANG H L, WANG S B,et al. Ru-doped Li4Ti5O12 anode materials for high rate lithium-ion batteries. J. Power Sources, 2013, 228(11): 244-249.
[48]	SUBBURAJ T, PRASANNA K, KIM K J,et al. Structural and electrochemical evaluation of bismuth doped lithium titanium oxides for lithium ion batteries. J. Power Sources, 2015, 280: 23-29.
[49]	HUANG P X, TANG S H, PENG H,et al. In-situ synthesis of graphitized-carbon coated Li4Ti5O12/C anode for high-rate lithium ion batteries. Mater. Sci. Forum, 2015, 814: 358-364.
[50]	WANG X Y, SHEN L F, LI H S,et al. PEDOT coated Li4Ti5O12 nanorods: soft chemistry approach synthesis and their lithium storage properties. Electrochim. Acta, 2014, 129(16): 283-289.
[51]	MU D B, CHEN Y J, WU B R,et al. Nano-sized Li4Ti5O12/C anode material with ultrafast charge/discharge capability for lithium ion batteries. J. Alloys Compd., 2016, 671: 157-163.
[52]	KUO Y C, LIN J Y.One-pot Sol-Gel synthesis of Li4Ti5O12/C anode materials for high-performance Li-ion batteries.Electrochim. Acta, 2014, 142: 43-50.
[53]	GAO L, LIU R J, HU H,et al. Carbon-decorated Li4Ti5O12/rutile TiO2 mesoporous microspheres with nanostructures as high-performance anode materials in lithium-ion batteries. Nanotechnology, 2014, 25(17): 175402-175410.
[54]	XUE R, YAN J W, JIANG L,et al. Fabrication of lithium titanate/ graphene composites with high rate capability as electrode materials for hybrid electrochemical super capacitors. Mater. Chem. Phys., 2015, 160: 375-382.
[55]	LI R Y, CHEN T Y, SUN B B,et al. Novel lithium titanate-graphene hybrid containing two graphene conductive frameworks for lithium- ion battery with excellent electrochemical performance. Mater. Res. Bull., 2015, 70: 965-975.
[56]	YANG X J, ZHENG A B, WANG X L,et al. Graphene nanosheet and carbon layer co-decorated Li4Ti5O12 as high performance anode material for rechargeable lithium-ion batteries. Ceram. Int., 2017, 43(3): 3252-3258.
[57]	KIM J, LEE K E, KIM K H,et al. Single-layer graphene-wrapped Li4Ti5O12 anode with superior lithium storage capability. Carbon, 2017, 114: 275-283.
[58]	KIM K T, YU C Y, YOON C S,et al. Carbon-coated Li4Ti5O12 nanowires showing high rate capability as an anode material for rechargeable sodium batteries. Nano Energy, 2015, 12: 725-734.
[59]	LUO H J, SHEN L F, RUI K,et al. Carbon coated Li4Ti5O12 nanorods as superior anode material for high rate lithium ion batteries. J. Alloys Compd., 2013, 572: 37-42.
[60]	LIU J, SONG K, AKEN P A,et al. Self-supported Li4Ti5O12-C nanotube arrays as high-rate and long-life anode materials for flexible Li-ion batteries. Nano Lett., 2014, 14(5): 2597-2603.

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]