Boosting Cycling Stability and Rate Capability of Li–CO₂ Batteries via Synergistic Photoelectric Effect and Plasmonic Interaction

Abstract

Sluggish CO 2 reduction/evolution kinetics at cathodes seriously impede the realistic applications of Li-CO 2 batteries. Herein, synergistic photoelectric effect and plasmonic interaction are introduced to accelerate CO 2 reduction/evolution reactions by designing a silver nanoparticle-decorated titanium dioxide nanotube array cathode. The incident light excites energetic photoelectrons/holes in titanium dioxide to overcome reaction barriers, and induces the intensified electric field around silver nanoparticles to enable effective separation/transfer of photogenerated carriers and a thermodynamically favorable reaction pathway. The resulting Li-CO 2 battery demonstrates ultra-low charge voltage of 2.86 V at 0.10 mA cm À 2 , good cycling stability with 86.9 % round-trip efficiency after 100 cycles, and high rate capability at 2.0 mA cm À 2 . This work offers guidance on rational cathode design for advanced Li-CO 2 batteries and beyond.

Metal-related electrocatalysts for Li–CO2batteries: an overview of the fundamentals to explore future-oriented strategies

“…159 At the same time, the photoelectric effect and the plasma interaction have synergistic effects, and the locally enhanced electric field has a strong promoting effect on the separation and transfer of photogenerated carriers, so the full utilization of carriers in the reduction and oxidation of CO 2 is realized. 79 In conclusion, the photoelectric effect and plasmonic interactions are expected to play crucial roles in Li–CO 2 battery catalytic systems.…”

Highly Efficient Cu‐Porphyrin‐Based Metal–Organic Framework Nanosheet as Cathode for High‐Rate Li‐CO2 Battery

“…[11][12][13] Therefore, to achieve the purpose of reducing polarization, increasing energy efficiency and cycle life, researchers have designed efficient cathodic catalysts, [14][15][16] electrolyte additives, [17][18][19] quasi-solid electrolyte, [20,21] and proposed a novel photoassisted system in Li-CO 2 batteries. [22,23] As for the design of solid phase catalysts, the noble metal-based catalysts with a high proportion of d electrons specially involved in coordination show excellent catalytic performance in various fields. [24][25][26][27][28] Unfortunately, the low natural abundance has limited the application on large scale for economical consideration.…”

Aprotic Lithium‐Carbon Dioxide Batteries: Reaction Mechanism and Catalyst Design

“…Through the effect of semiconductor photocatalysis, the charging voltage of Li-O 2 battery can be effectively reduced, and the energy efficiency is even more than 100%. [108][109][110][111][112][113][114] Zhang et al [115] prepared TiO 2 nanotube arrays modified with silver nanoparticles as cathode. High-energy photoelectrons/holes in TiO 2 reduce the reaction energy barrier, and introduction of the silver nanoparticles can accelerate the effective separation/transfer of photocarriers, which ultimately promotes the thermodynamically favorable reaction.…”

“…Through the effect of semiconductor photocatalysis, the charging voltage of Li‐O 2 battery can be effectively reduced, and the energy efficiency is even more than 100% [108–114] . Zhang et al [115] . prepared TiO 2 nanotube arrays modified with silver nanoparticles as cathode.…”