Titanium Niobium Oxide Ti₂Nb₁₀O₂₉/Carbon Hybrid Electrodes Derived by Mechanochemically Synthesized Carbide for High‐Performance Lithium‐Ion Batteries

Abstract

This work introduces the facile and scalable two-step synthesis of Ti 2 Nb 10 O 29 (TNO)/carbon hybrid material as a promising anode for lithium-ion batteries (LIBs). The first step consisted of a mechanically induced self-sustaining reaction via ball-milling at room temperature to produce titanium niobium carbide with a Ti and Nb stoichiometric ratio of 1 to 5. The second step involved the oxidation of as-synthesized titanium niobium carbide to produce TNO. Synthetic air yielded fully oxidized TNO, while annealing in CO 2 resulted in TNO/carbon hybrids. The electrochemical performance for the hybrid and non-hybrid electrodes was surveyed in a narrow potential window (1.0-2.5 V vs. Li/Li +) and a large potential window (0.05-2.5 V vs. Li/ Li +). The best hybrid material displayed a specific capacity of 350 mAh g À 1 at a rate of 0.01 A g À 1 (144 mAh g À 1 at 1 A g À 1) in the large potential window regime. The electrochemical performance of hybrid materials was superior compared to non-hybrid materials for operation within the large potential window. Due to the advantage of carbon in hybrid material, the rate handling was faster than that of the non-hybrid one. The hybrid materials displayed robust cycling stability and maintained ca. 70 % of their initial capacities after 500 cycles. In contrast, only ca. 26 % of the initial capacity was maintained after the first 40 cycles for non-hybrid materials. We also applied our hybrid material as an anode in a full-cell lithium-ion battery by coupling it with commercial LiMn 2 O 4 .

Porous Mixed-Metal Oxide Li-Ion Battery Electrodes by Shear-Induced Co-assembly of Precursors and Tailored Polymer Particles

“…A broad process at the lower potential region from 1.0 to 1.5 V vs Li/Li + is ascribed to the second redox process of Nb 4+ /Nb 3+ . However, this transition is not completely lithiated at this potential range . When the lower potential limit is extended to 0.01 V vs Li/Li + , two new reduction processes at 0.83 and 0.69 V vs Li/Li + , assigned to the solid electrolyte interface (SEI) formation due to electrolyte decomposition and complete lithiation process, respectively .…”

“…However, this transition is not completely lithiated at this potential range. 65 When the lower potential limit is extended to 0.01 V vs Li/Li + , two new reduction processes at 0.83 and 0.69 V vs Li/Li + , assigned to the solid electrolyte interface (SEI) formation due to electrolyte decomposition and complete lithiation process, respectively. 66 The corresponding oxidation peak is observed at ca.…”

“…The initial capacity of 7002hCO 2 IR represents 84% of the theoretical capacity of Ti 2 Nb 10 O 29 , which corresponds to the highest reported for TNO at this potential range. 65,68 Considering that TNO makes up only 53% of the active material composition, such performance is impressive since both T-Nb 2 O 5 and TiO 2 provide much lower theoretical capacities (202 and 330 mAh•g −1 , respectively). 69 As observed previously in the cyclic voltammetry, when the lower potential limit is extended to 0.01 V vs Li + /Li, an initial higher capacity is achieved due to SEI formation.…”

Advanced and Emerging Negative Electrodes for Li-Ion Capacitors: Pragmatism vs. Performance

“…Budak et al further improved the performance of this anode material through a composite of Ti 2 Nb 10 O 29 with carbon [57]. Preliminary results in half cells (vs. Li metal) demonstrated a 350 mAh g −1 at a rate of 0.01 A g −1 (144 mAh g −1 at 1 A g −1 ), illustrating the potential of this material for LICs.…”

Lithium‐Ion and Sodium‐Ion Hybrid Capacitors: From Insertion‐Type Materials Design to Devices Construction

“…presented a scalable synthesis method of Ti 2 Nb 10 O 29 /carbon hybrid by annealing titanium niobium carbide in CO 2 ambient. [ 52 ] The highest capacity of 350 mAh g −1 can be achieved at 10 mA g −1 in the potential window of 0.05–2.5 V.…”