Cations Distribution and Valence States in Mn-Substituted Li4Ti5O12 Structure

Capsoni, Doretta; Bini, Marcella; Massarotti, Vincenzo; Mustarelli, Piercarlo; Chiodelli, Gaetano; Azzoni, C. B.; Mozzati, Maria Cristina; Linati, Laura; Ferrari, Stefania

doi:10.1021/cm703650c

Cited by 58 publications

(58 citation statements)

References 42 publications

(98 reference statements)

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“…One is poor electronic and ionic conductivity, which leads to poor rate capability. 3,4 In addition, a number of strategies have been implemented to overcome the low electrical conductivity and to further improve the power performance of Li 4 Ti 5 O 12 , including nanosized materials, [5][6][7] design of unique configurations, [8][9][10][11] carbon coating, [12][13][14] 3d-elements doping at Ti sites, [15][16][17] rare earth doping, 18 and coating with noble metal nano-particles, oxides or high conductive phase such as Ag 19 , Cu 2 O 20 and TiN phase, 3 which are expected to solve the challenge with good cyclic performance as well as to maintain a high rate performance.…”

mentioning

confidence: 99%

Dual Functions of Carbon in Li₄Ti₅O₁₂/C Microspheres

Lei

Wu²,

Luo

et al. 2014

J. Electrochem. Soc.

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Spinel Li 4 Ti 5 O 12 has become an alternative material to replace graphite anodes in terms of solving safety issues and improving battery life-time. Unfortunately, as Li 4 Ti 5 O 12 is an insulator, the low electrical conductivity becomes a major drawback, as it is unfavorable to higher rate capability. In addition to the low electronic conductivity, severe gassing during charge/discharge cycles is a critical but often-overlooked problem of Li 4 ExperimentalMaterials synthesis.-Anatase TiO 2 (220 nm in average particle diameter and 99.5% in purity, Hangzhou Wanjing New Material Co., Ltd) and Li 2 CO 3 (99.9% in purity, Shanghai China Lithium Industrial Co., Ltd.) were used as raw materials. The starting coarse Li 4 Ti 5 O 12 was prepared by a solid-state reaction method as described in a previous work. 26,27 The stoichiometric amounts of Li 2 CO 3 and anatase TiO 2 with molar ratio of Li: Ti = 0.82:1 were mixed with ethanol as dispersant by planetary ballmilling. The ball-milled mixture was heated in a furnace at 800• C in air for 18 h to obtain the coarse materials were first ball-milled without a carbon source and with 5 wt% pitch as a carbon source using water as a dispersant for 1.5 h, respectively. The resultant slurry was then spray dried to obtain the precursors individually. Finally, two precursors were all annealed at 650• C for 6 h in an Ar atmosphere to obtain the final materials.Characterization.-X-ray diffraction (XRD) patterns of the samples were recorded on a Rigaku diffractometer using Cu Kα irradiation. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images were obtained on a Nova NanoSEM 430 and Tecnai F20.

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mentioning

confidence: 99%

Dual Functions of Carbon in Li₄Ti₅O₁₂/C Microspheres

Lei

Wu²,

Luo

et al. 2014

J. Electrochem. Soc.

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“…Donor doping with high valence elements substituting for Li [17,48,54,55]. In addition, the isovalent doping of Na for Li [56,57] [41,42,60]. In spinel Li 4 Ti 5 O 12 , the same Li ions take two different sites (8a and 16d) while the same 16d sites are occupied with two different ions (Li and Ti).…”

Section: Lattice Dopingmentioning

confidence: 99%

Lithium Titanate-Based Anode Materials

Zhao

2015

Rechargeable Batteries

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Graphitic carbon is the most widely used anode material in commercial Li-ion batteries due to its low lithiation potential, long cycle life, abundant resources and low cost. However, Li-ion batteries using graphite as anode material give rise to rate, safety and life problems. During lithium intercalation/deintercalation process, graphite undergoes a considerable volume change (*10 % [1]), which could cause particle cracking and even peeling off of anode film from the current collector, leading to gradual capacity degradation of the electrode [2,3]. Safety concerns arise when the cells experience fast charging, long-term cycling, or low temperature charging owing to the propensity of formation of lithium dendrites, which is induced by the low lithiation potential of the graphite anode (close to 0 V vs. Li/Li + ) and the low lithium ion diffusivity in the graphite lattice [4,5]. As an alternative anode material to carbon, Li 4 Ti 5 O 12 has been extensively studied for the potential use in large-scale Li-ion batteries. Li 4 Ti 5 O 12 shows stable charge/discharge platform at ca. 1.55 V versus Li/Li + , and possesses excellent cycling stability and unique safety characteristic owing to its negligible volume change and high redox potential upon Li-ion intercalation/deintercalation. However, coarse Li 4 Ti 5 O 12 exhibits poor rate performance because of its low electronic conductivity and sluggish lithium ion diffusivity [6,7]. In some cases, especially when aging at elevated temperature or cycling in a long-term regime, gas generation frequently occurs in Li 4 Ti 5 O 12 -based batteries [8]. In past decades, many efforts have been devoted to overcoming these problems and significant advancements have been achieved, which make Li 4 Ti 5 O 12 viable for practical application in batteries for various electrical energy storage, such as electric/hybrid electric/plug-in hybrid electric vehicles (EV/HEV/PHEV), grid load leveling, integration of renewable energy sources, etc.

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“…In order to improve the electrochemical performance of the Li 4 Ti 5 O 12 anode, extensive works concentrated on forming nanoparticles [14][15][16][17], doping [18][19][20][21][22][23] with metal cations and composing with carbon or metal powders [21,[24][25][26][27][28][29]. The formation of nanoparticles can reduce the Li-ion diffusion path as well as provide a large contact area between the nanoparticles.…”

Section: -10mentioning

confidence: 99%

Properties of Li4Ti5O12 as an anode material in non-flammable electrolytes

Kurc

Swiderska‐Mocek

2013

J Appl Electrochem

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Two non-flammable electrolytes 1 M LiPF 6 in sulfolane (TMS) ? 5 wt% VC and 0.7 M lithium bis(trifluoromethanesulphonyl)imide (LiNTf 2 ) in N-methyl-Npropylpyrrolidinium bis(trifluoromethanesulphonyl)imide (MePrPyrNTf 2 ) ? 10 wt% gamma-butyrolactone (GBL) were tested with Li 4 Ti 5 O 12 (LTO) as highly promising anode material for application in lithium-ion batteries. The results were compared for the titanium anode in the classic electrolyte: 1 M LiPF 6 in propylene carbonate ? dimethyl carbonate (PC ? DMC, 1:1). The performances of LTO/ electrolyte/Li cell were tested using cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge and scanning electron microscopy (SEM). SEM images of electrodes and those taken after electrochemical cycling showed changes which may be interpreted as a result of solid-state interface formation. Good charge/discharge capacities and low capacity loss at medium C rates preliminary cycling was obtained for the Li 4 Ti 5 O 12 anode. For LTO/1 M LiPF 6 in PC ? DMC/Li system, the best capacity was obtained at C/10 and C/3 (145 and 154 mAh g -1 , respectively). In the case of a system working on the basis of a TMS solution (1 M LiPF 6 in TMS ? 5 wt% VC) the best value was obtained at a C/5 current and an average of more than 150 mAh g -1 (86 % of theoretical capacity). For the 0.7 M LiNTf 2 in MePrPyrNTf 2 ? 10 wt% GBL electrolyte, the highest capacitance value (at C/20 current) of about 150 mAh g -1 was observed. The 1 M LiPF 6 in TMS ? 5 wt% VC and 0.7 M LiNTf 2 in MePrPyrNTf 2 ? 10 wt% GBL electrolytes had a relatively broad thermal stability range and no decomposition peak was observed below 150°C.

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Cations Distribution and Valence States in Mn-Substituted Li₄Ti₅O₁₂ Structure

Cited by 58 publications

References 42 publications

Dual Functions of Carbon in Li₄Ti₅O₁₂/C Microspheres

Dual Functions of Carbon in Li₄Ti₅O₁₂/C Microspheres

Lithium Titanate-Based Anode Materials

Properties of Li4Ti5O12 as an anode material in non-flammable electrolytes

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Cations Distribution and Valence States in Mn-Substituted Li4Ti5O12 Structure

Cited by 58 publications

References 42 publications

Dual Functions of Carbon in Li4Ti5O12/C Microspheres

Dual Functions of Carbon in Li4Ti5O12/C Microspheres

Lithium Titanate-Based Anode Materials

Properties of Li4Ti5O12 as an anode material in non-flammable electrolytes

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Cations Distribution and Valence States in Mn-Substituted Li₄Ti₅O₁₂ Structure

Dual Functions of Carbon in Li₄Ti₅O₁₂/C Microspheres

Dual Functions of Carbon in Li₄Ti₅O₁₂/C Microspheres