Synthesis of Mesoporous Lithium Titanate Thin Films and Monoliths as an Anode Material for High‐Rate Lithium‐Ion Batteries

Balcı, Fadime Mert; Kudu, Ömer Ulaş; Yılmaz, Eda; Dag, Ömer

doi:10.1002/chem.201604253

Cited by 6 publications

(5 citation statements)

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“…The large surface area might increase the interface of the active material and electrolyte, thus facilitating the Li + ion transport. Moreover, its mesoporous structure is believed to favor ion diffusion and allow easy permeability of the electrolyte. , Urchin-VS 4 demonstrates 3D structures with many long nanowires emanating from the core. The nanowires also provide shortened diffusion length and large interfacial area of the active material and the electrolyte.…”

Section: Resultsmentioning

confidence: 99%

High-Crystallinity Urchin-like VS₄ Anode for High-Performance Lithium-Ion Storage

Yuan

Zhang

Feng

et al. 2018

ACS Appl. Mater. Interfaces

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VS4 anode materials with controllable morphologies from hierarchical microflower, octopus-like structure, seagrass-like structure to urchin-like structure have been successfully synthesized by a facile solvothermal synthesis approach using different alcohols as solvents. Their structures and electrochemical properties with various morphologies are systematically investigated, and the structure–property relationship is established. Experimental results reveal that Li+ ion storage behavior in VS4 significantly depends on physical features such as the morphology, crystallite size, and specific surface area. According to this study, electrochemical performance degrades on the order of urchin-like VS4 > octopus-like VS4 > seagrass-like VS4 > flower-like VS4. Among them, urchin-like VS4 demonstrates the best electrochemical performance benefiting from its peculiar structure which possesses large surface area that accommodates the volume change to a certain extent, and single-crystal thorns that provide fast electron transportation. Kinetic parameters derived from EIS spectra and sweep-rate-dependent CV curves, such as charge-transfer resistances, Li+ ion apparent diffusion coefficients and stored charge ratio of capacitive and intercalation contributions, both support this claim well. In addition, the EIS measurement was conducted during the first discharge/charge process to study the solid electrolyte interface (SEI) formation on urchin-like VS4 and kinetics behavior of Li+ ion diffusion. A better fundamental understanding on Li+ storage behavior in VS4 is promoted, which is applicable to other vanadium-based materials as well. This study also provides invaluable guidance for morphology-controlled synthesis tailored for optimal electrochemical performance.

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Section: Resultsmentioning

confidence: 99%

High-Crystallinity Urchin-like VS₄ Anode for High-Performance Lithium-Ion Storage

Yuan

Zhang

Feng

et al. 2018

ACS Appl. Mater. Interfaces

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“…Molten salt-assisted self-assembly (MASA) [32][33][34][35] is an effective so-templating process to synthesize sponge like mesoporous thin lms. Similar to evaporation induced self-assembly (EISA), [36][37][38] a clear mixture of ingredients is coated over a substrate, followed by calcination at an elevated temperature in the MASA approach.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of mesoporous LiMn₂O₄and LiMn_2−xCo_xO₄thin films using the MASA approach as efficient water oxidation electrocatalysts

et al. 2018

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“…Molten salt‐assisted self‐assembly (MASA) is an important synthesis process used to fabricate mesoporous transparent thin films of metal oxides . The method has been first employed to produce mesoporous CdO and ZnO coated silica, where the CdO and ZnO can be homogeneously coated over silica pore‐walls as thin as 1.6 nm .…”

Section: Introductionmentioning

confidence: 99%

“…The method has been first employed to produce mesoporous CdO and ZnO coated silica, where the CdO and ZnO can be homogeneously coated over silica pore‐walls as thin as 1.6 nm . Later, many mesoporous metal titanates (CdTiO 3 , Zn 2 TiO 4 , CoTiO 3 , MnTiO 3 , and Li 4 Ti 5 O 12 ) have been synthesized using the MASA method . In this process, both ethanol (or water in some cases) and the salt species act as two different solvents to dissolve and to assemble surfactants into the mesophases, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…A silica or titania source is added to the media, where their polymerization starts in the solution phase and enhances with coating to form the gel phase. During the process, two surfactants (charged and neutral) are also required to form stable mesophases with high salt concentrations . Mesoporous materials prepared, up to now, using the MASA process have always been carried out in the presence of a polymerizing agent (metal alkoxides) …”

Section: Introductionmentioning

confidence: 99%

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Molten Salt Assisted Self‐Assembly: Synthesis of Mesoporous LiCoO₂ and LiMn₂O₄ Thin Films and Investigation of Electrocatalytic Water Oxidation Performance of Lithium Cobaltate

Saat

Balcı

Alsaç

et al. 2017

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the literature, the synthesis of mesoporous metal oxides and metal lithiates has always been a challenge. Many strategies for synthesis, including hard and soft templating methods, have been developed over the years. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] The lyotropic liquid crystalline (LLC) templating method has also been employed to produce metals and metal oxides with the help of a reducing agent or electrochemical methods. [21][22][23][24][25] Unfortunately, the many existing metal ion precursors are not appropriate for use in soft and hard templating. There are some successful examples of the synthesis of mesoporous metal oxides by using alkoxy precursors. [26][27][28][29][30] However, most metal precursors are common ion salts, such as metal chlorides, nitrates, sulfates, and acetates, that need high temperatures to undergo hydrolysis and condensation reactions to form their oxides. Even if one can incorporate the salts into mesophases, in the next step, in going from salt precursors to oxides, the salt species shrink by 70-90%, which causes a collapse of the meso-order in soft templating processes or a nonuniform coating in the hardtemplating cases. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] There are no examples of mesoporous thin films produced through hard-templating and there has been limited success with soft templating methods. In particular, the oxides that contain two or more metals are even more difficult to assemble into mesoporous materials. It is still extremely challenging to form and maintain mesostructures in most metal based materials.Although, there are some successful examples of mesoporous metal lithiates powders, using hard templating method, [15][16][17][18][19][20] the method is quite complex and generally impossible to produce thin films. Bruce and co-workers reported the first synthesis of mesoporous low temperature spinel LiCoO 2 and LiCoO 2 nanowires. [31] The synthesis of mesoporous spinel LiMn 2 O 4 has been reported by Luo et al. [32] Hwang et al. obtained the mesoporous metal lithiates by using soft templating. [33] The resulting material had a 3.8 nm pore size, 31 nm wall thickness, and 13.8 m 2 g −1 surface area. [34] . The method described can be adopted to synthesize other metal oxides and metal lithiates. The mesoporous thin films of LiCoO 2 show promising performance as water oxidation catalysts under pH 7 and 14 conditions. The electrodes, prepared using CTAN as the cosurfactant, display the lowest overpotentials in the literature among other LiCoO 2 systems, as low as 376 mV at 10 mA cm -2 and 282 mV at 1 mA cm -2 . Mesoporous Thin Films

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Synthesis of Mesoporous Lithium Titanate Thin Films and Monoliths as an Anode Material for High‐Rate Lithium‐Ion Batteries

Cited by 6 publications

References 46 publications

High-Crystallinity Urchin-like VS₄ Anode for High-Performance Lithium-Ion Storage

High-Crystallinity Urchin-like VS₄ Anode for High-Performance Lithium-Ion Storage

Synthesis of mesoporous LiMn₂O₄and LiMn_2−xCo_xO₄thin films using the MASA approach as efficient water oxidation electrocatalysts

Molten Salt Assisted Self‐Assembly: Synthesis of Mesoporous LiCoO₂ and LiMn₂O₄ Thin Films and Investigation of Electrocatalytic Water Oxidation Performance of Lithium Cobaltate

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Synthesis of Mesoporous Lithium Titanate Thin Films and Monoliths as an Anode Material for High‐Rate Lithium‐Ion Batteries

Cited by 6 publications

References 46 publications

High-Crystallinity Urchin-like VS4 Anode for High-Performance Lithium-Ion Storage

High-Crystallinity Urchin-like VS4 Anode for High-Performance Lithium-Ion Storage

Synthesis of mesoporous LiMn2O4and LiMn2−xCoxO4thin films using the MASA approach as efficient water oxidation electrocatalysts

Molten Salt Assisted Self‐Assembly: Synthesis of Mesoporous LiCoO2 and LiMn2O4 Thin Films and Investigation of Electrocatalytic Water Oxidation Performance of Lithium Cobaltate

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Product

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High-Crystallinity Urchin-like VS₄ Anode for High-Performance Lithium-Ion Storage

High-Crystallinity Urchin-like VS₄ Anode for High-Performance Lithium-Ion Storage

Synthesis of mesoporous LiMn₂O₄and LiMn_2−xCo_xO₄thin films using the MASA approach as efficient water oxidation electrocatalysts

Molten Salt Assisted Self‐Assembly: Synthesis of Mesoporous LiCoO₂ and LiMn₂O₄ Thin Films and Investigation of Electrocatalytic Water Oxidation Performance of Lithium Cobaltate