Carbon-coated, hierarchically mesoporous TiO2 microparticles as an anode material for lithium and sodium ion batteries

• Published in: Electrochimica acta 2019-10, Vol.321, p.134639, Article 134639
• Main Authors: Devina, Winda, Nam, Dongho, Hwang, Jieun, Chandra, Christian, Chang, Wonyoung, Kim, Jaehoon
• Format: Article
• Language: English
• Subjects: Anatase; Anatase TiO2; Anodes; Battery cycles; Carbon; Citric acid; Crystal growth; Crystallites; Electrochemical analysis; Electrode materials; Electrolytes; Ethylene glycol; Heat treatment; Li-ion batteries; Lithium; Lithium-ion batteries; Microparticles; Na-ion batteries; Nanoparticles; Oleic acid; Rechargeable batteries; Sodium-ion batteries; Supercritical fluids; Supercritical methanol; Surface modifiers; Titanium dioxide
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2019.134639

Hierarchically porous anatase TiO2 microparticles are synthesized in supercritical methanol (scMeOH) in the presence of organic surface modifiers such as oleylamine, oleic acid, and poly(ethylene glycol)methyl ether/citric acid (PEGME/CA) mixture. Primary TiO2 nanoparticles (5–9 nm) that loosely aggregate to form secondary micron-sized particles (0.2–1.5 μm) are obtained in the presence of PEGME/CA. The surface modifier aids the effective suppression of undesirable crystal growth because their molecules cap the surfaces of growing particles in scMeOH. An ultrathin, conformal and uniform carbon layer with 1–2 nm thickness is then formed on the surface of the TiO2 particles by heat treatment. The carbon-coated TiO2 particles delivers 231 mAh g−1 at 0.1 C after 50 cycles and 85 mAh g−1 at 10 C in a lithium-ion battery cell, 275 mAh g−1 at 0.1 C after 50 cycles, 40 mAh g−1 at 10 C, and high capacity retention of 94% after 450 cycles in a sodium-ion battery cell. The excellent electrochemical performance of the TiO2 particles is attributed to the small crystallite size, continuous electronic network formed by the close contact of individual carbon-coated primary TiO2 particles, and the effective penetration of the mesopores by the electrolytes. [Display omitted] •Hierarchically porous anatase TiO2 microparticles synthesized in sc-methanol.•Nanosized TiO2 particles were carbon-coated using organic surface modifiers.•The fast nucleation and carbon coating reduced the crystal growth.•Small crystallite size and electronic network enhanced electrochemical performance.•As an anode in NIBs, 275 mAh g−1 at 0.1 C and 40 mAh g−1 at 10 C were delivered.