Three-Dimensionally Ordered Macroporous Li4Ti5O12:  Effect of Wall Structure on Electrochemical Properties

Sorensen, Erin M.; Barry, Scott J.; Jung, Ha Kyun; Rondinelli, James R.; Vaughey, John T.; Poeppelmeier, Kenneth R.

doi:10.1021/cm052203y

Cited by 291 publications

(134 citation statements)

References 66 publications

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“…Since then several more electroactive materials have been synthesized in the inverse-opal form and explored as both positive [24][25][26] and negative electrodes. [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42] In most cases the use of inverse opals led to an improvement in rate capabilities and often to better cycling behavior of the materials. Composite materials based on inverse-opal structures have been also suggested to be used as lithium ion battery electrodes.…”

Section: Introductionmentioning

confidence: 99%

Silicon Inverse‐Opal‐Based Macroporous Materials as Negative Electrodes for Lithium Ion Batteries

Esmanski

Ozin

2009

Adv Funct Materials

263

214

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Several types of silicon‐based inverse‐opal films are synthesized, characterized by a range of experimental techniques, and studied in terms of electrochemical performance. Amorphous silicon inverse opals are fabricated via chemical vapor deposition. Galvanostatic cycling demonstrates that these materials possess high capacities and reasonable capacity retentions. Amorphous silicon inverse opals perform unsatisfactorily at high rates due to the low conductivity of silicon. The conductivity of silicon inverse opals can be improved by their crystallization. Nanocrystalline silicon inverse opals demonstrate much better rate capabilities but the capacities fade to zero after several cycles. Silicon–carbon composite inverse‐opal materials are synthesized by depositing a thin layer of carbon via pyrolysis of a sucrose‐based precursor onto the silicon inverse opals. The amount of carbon deposited proves to be insufficient to stabilize the structures and silicon–carbon composites demonstrate unsatisfactory electrochemical behavior. Carbon inverse opals are coated with amorphous silicon producing another type of macroporous composite. These electrodes demonstrate significant improvement both in capacity retentions and in rate capabilities. The inner carbon matrix not only increases the material conductivity but also results in lower silicon pulverization during cycling.

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Section: Introductionmentioning

confidence: 99%

Silicon Inverse‐Opal‐Based Macroporous Materials as Negative Electrodes for Lithium Ion Batteries

Esmanski

Ozin

2009

Adv Funct Materials

263

214

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“…Further improvement can be achieved by introducing high porosity and high specific surface area. 47,48 The mesoporous materials offer fast ion/electron transfer and sufficient contact between active materials and electrolyte, resulting in a large lithium storage capacity and high insertion rates. CMK-3, a highly conductive mesoporous carbon with desirable characteristics, has attracted much attention for used as conductive and porous matrix for LIBs.…”

Section: ■ Introductionmentioning

confidence: 99%

Three-Dimensional Coherent Titania–Mesoporous Carbon Nanocomposite and Its Lithium-Ion Storage Properties

Shen

Uchaker

Cheng

et al. 2012

ACS Appl. Mater. Interfaces

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Mesoporous, micro/nanosized TiO 2 /C composites with uniformly dispersed TiO 2 nanoparticles embedded in a carbon matrix have been rationally designed and synthesized. In brief, TiO 2 precursor was infiltrated into the channels of surfaceoxidized mesoporous carbon (CMK-3) by means of electrostatic interaction, followed by in situ hydrolysis and growth of TiO 2 nanocrystallites, resulting in ultrafine TiO 2 nanoparticle confined inside the channels of mesopores carbon. ■ INTRODUCTIONLithium ion batteries (LIBs) have been regarded as one of the most promising candidates for applications in electric and hybrid vehicles with the potential to save oil and reduce CO 2 emissions, although they still suffer from low power density and safety concerns. 1−4 Conventional graphitic carbons used as anodes in commercial LIBs exhibits poor rate performance induced by its low Li diffusion coefficient. 5 Because of the lower operating voltage, solid-electrolyte interface (SEI) film and dendritic lithium are easily formed on the surface of graphite anode, which would cause serious safety issues and poor cycle life. 6−10 The commercial LIBs are inadequate to meet high power applications, advanced materials with better safety and high rate capability are critical for next-generation LIBs.Titanium-based compounds are promising candidates as alternative materials to carbonaceous anodes, because of not only its structural characteristics and special surface activity but also its low cost, safety, and environmental benignity. 11−18 Typically, the Li + insertion/extraction reaction for TiO 2 polymorphs occurs in the potential range of 1.4−1.8 V vs Li/ Li + , according to the following reactionBecause of low packing density, anatase (density, ρ = 3.89 g cm −3 ) and TiO 2 −B (ρ = 3.73 g cm −3 ) phases show higher lithium storage capacity as compared to densely packed brookite (ρ = 4.13 g cm −3 ) and rutile (ρ = 4.25 g cm −3 ) phases, both anatase TiO 2 and TiO 2 −B have been extensively investigated as potential alternative anode material for LIBs. 19,20 Anatase TiO 2 is known to be a electrochemically active with a capacity of about 0.6 lithium ion in Li x TiO 2 at 1.78 V vs Li/Li + . TiO 2 −B is the least dense polymorph of TiO 2 , and has a theoretical capacity of 335 mA h g −1 . TiO 2 −B has an open structure with freely accessible channels for Li-ion transport perpendicular to the (010) Unfortunately, the rate performance of bulk titania and Li 4 Ti 5 O 12 material is greatly limited due to the poor electronic and ionic conductivity, which constitutes a major obstacle for

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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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Three-Dimensionally Ordered Macroporous Li₄Ti₅O₁₂: Effect of Wall Structure on Electrochemical Properties

Cited by 291 publications

References 66 publications

Silicon Inverse‐Opal‐Based Macroporous Materials as Negative Electrodes for Lithium Ion Batteries

Silicon Inverse‐Opal‐Based Macroporous Materials as Negative Electrodes for Lithium Ion Batteries

Three-Dimensional Coherent Titania–Mesoporous Carbon Nanocomposite and Its Lithium-Ion Storage Properties

Dual Functions of Carbon in Li₄Ti₅O₁₂/C Microspheres

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Three-Dimensionally Ordered Macroporous Li4Ti5O12: Effect of Wall Structure on Electrochemical Properties

Cited by 291 publications

References 66 publications

Silicon Inverse‐Opal‐Based Macroporous Materials as Negative Electrodes for Lithium Ion Batteries

Silicon Inverse‐Opal‐Based Macroporous Materials as Negative Electrodes for Lithium Ion Batteries

Three-Dimensional Coherent Titania–Mesoporous Carbon Nanocomposite and Its Lithium-Ion Storage Properties

Dual Functions of Carbon in Li4Ti5O12/C Microspheres

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Three-Dimensionally Ordered Macroporous Li₄Ti₅O₁₂: Effect of Wall Structure on Electrochemical Properties

Dual Functions of Carbon in Li₄Ti₅O₁₂/C Microspheres