Realizing Interfacial Electronic Interaction within ZnS Quantum Dots/N‐rGO Heterostructures for Efficient Li–CO₂ Batteries

Abstract

With high theoretical energy density, rechargeable metal–gas batteries (e.g., Li–CO2 battery) are considered as one of the most promising energy storage devices. However, their practical applications are hindered by the sluggish reaction kinetics and discharge product accumulation during battery cycling. Currently, the solutions focus on exploration of new catalysts while the thorough understanding of their underlying mechanisms is often ignored. Herein, the interfacial electronic interaction within rationally designed catalysts, ZnS quantum dots/nitrogen‐doped reduced graphene oxide (ZnS QDs/N‐rGO) heterostructures, and their effects on transformation and deposition of discharge products in the Li–CO2 battery are revealed. In this work, the interfacial interaction can both enhance the catalytic activities of ZnS QDs/N‐rGO heterostructures and induce the nucleation of discharge products to form a homogeneous Li2CO3/C film with excellent electronic transmission and high electrochemical activities. When the batteries cycle within a cutoff specific capacity of 1000 mAh g−1 at a current density of 400 mA g−1, the cycling performance of the Li–CO2 battery using a ZnS QDs/N‐rGO cathode is over 3 and 9 times than those coupled with a ZnS nanosheets (NST)/N‐rGO cathode and a N‐rGO cathode, respectively. This work provides comprehensive understandings on designing catalysts for Li–CO2 batteries as well as other rechargeable metal–gas batteries.

Light/Electricity Energy Conversion and Storage for a Hierarchical Porous In2S3@CNT/SS Cathode towards a Flexible Li‐CO2 Battery

“…After recharge, there are only a few particles left on the surface of the ICS cathode. Furthermore, after discharge, there are three new peaks appear at 21.2°, 30.5°, and 31.6° in XRD patterns, corresponding to the planes of crystalline Li 2 CO 3 (Figure e) . During the reversible process, all characteristic peaks of Li 2 CO 3 disappear, while the ICS peaks appear again, suggesting that the deposition and decomposition of Li 2 CO 3 /C are highly reversible.…”

“…Rechargeable Li‐CO 2 batteries possess a high theoretical energy density of 1876 Wh kg −1 based on the reversible electrochemical reaction: 4 Li+3 CO 2 ↔2 Li 2 CO 3 +C ( E 0 =2.80 V vs. Li + /Li) . However, the insulation and immobility characteristics of bulk Li 2 CO 3 would lead to the sluggish kinetics of carbon dioxide reduction reaction (CDRR) and carbon dioxide evolution reaction (CDER), eventually resulting in the huge voltage gaps and low energy density of Li‐CO 2 batteries . Various electrocatalysts, such as carbon materials, noble metal‐based materials, transition‐metal‐based materials, metal–organic frameworks (MOFs), covalent organic frameworks (COFs), and redox mediators have been utilized to accelerate the kinetics of CDRR and CDER and improve the round‐trip efficiency, specific capacity, rate capability, and long‐term cycle performance of the Li‐CO 2 batteries .…”

Recent Advances in Lithium–Carbon Dioxide Batteries

“…The interfacial interaction could enhance the catalytic activity and induce the nucleation and growth of Li 2 CO 3 /C discharge products (Figure 9d). [ 98 ]…”

“…the nucleation and growth of Li 2 CO 3 /C discharge products (Figure 9d). [98] Ni was found to have a catalytic effect on the decomposition of Li 2 CO 3 . [99] A few years later, Zhang et al synthesized a CO 2 catalyst by dispersing Ni nanoparticles on N-doped graphene sheets.…”

Nano Polymorphism‐Enabled Redox Electrodes for Rechargeable Batteries

“…Among these metal-air batteries, Li-CO 2 batteries have received significant attention because they reuse CO 2 as a renewable energy carrier and reduce the anthropogenic CO 2 emissions. To date, a wide range of electrocatalysts, such as noble metal nanoparticles, [185] metal-organic frameworks, [186] covalent organic frameworks, [187] metal sulfides, [188,189] metal oxides, [190][191][192][193] metal carbides, [194][195][196] metal phosphides, [197] graphene/CNTs/carbon, [198][199][200][201][202] metal polyphthalocyanines, [203] and metal/carbon hybrids, [204][205][206][207][208][209][210] have been investigated for activating stabilized CO 2 , manipulating the discharge product distribution, and promoting reversibility in Li-CO 2 batteries. The main discharge products of the reduction process in Li-CO 2 batteries include Li 2 CO 3 and carbon.…”