High‐Performance, Long‐Life, Rechargeable Li–CO₂ Batteries based on a 3D Holey Graphene Cathode Implanted with Single Iron Atoms

Abstract

for CO 2 sequestration and environmental remediation, the utilization of CO 2 in metal (Li)-CO 2 batteries with a high theoretical specific capacity has recently attracted considerable attention. [3,4] Apart from the CO 2 sequestration, Li-CO 2 batteries offer an advantage for energy conversion and storage, particularly for exploration of the planet Mars with an atmosphere consisting of 96% CO 2 . [3] The driving force for energy conversion and storage in Li-CO 2 batteries is the reversible redox reaction between a lithium anode and CO 2 gas cathode to form/decompose Li 2 CO 3 during the discharge/charge processes. The sluggish CO 2 reduction and evolution reactions that take place at the air cathode often impede the kinetics of Li-CO 2 batteries, leading to a high voltage (>4.5 V vs Li/Li + ) for decomposing the discharge product (Li 2 CO 3 ). [5][6][7] Under such a high anodic potential, the electrolyte oxidation limits the energy efficiency and cycling life of the Li-CO 2 batteries. [5][6][7] Therefore, efficient A highly efficient cathode catalyst for rechargeable Li-CO 2 batteries is successfully synthesized by implanting single iron atoms into 3D porous carbon architectures, consisting of interconnected N,S-codoped holey graphene (HG) sheets. The unique porous 3D hierarchical architecture of the catalyst with a large surface area and sufficient space within the interconnected HG framework can not only facilitate electron transport and CO 2 /Li + diffusion, but also allow for a high uptake of Li 2 CO 3 to ensure a high capacity. Consequently, the resultant rechargeable Li-CO 2 batteries exhibit a low potential gap of ≈1.17 V at 100 mA g −1 and can be repeatedly charged and discharged for over 200 cycles with a cut-off capacity of 1000 mAh g −1 at a high current density of 1 A g −1 . Density functional theory calculations are performed and the observed appealing catalytic performance is correlated with the hierarchical structure of the carbon catalyst. This work provides an effective approach to the development of highly efficient cathode catalysts for metal-CO 2 batteries and beyond.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201907436.The overuse of fossil fuel has caused a rapid increase in CO 2 emissions and the associated severe environmental issues, including global warming, polar ice melting, sea level rising, rain acidification, and species extinction. [1,2] As a new strategy

Promoting the Electrocatalytic Activity of Ti3C2Tx MXene by Modulating CO2 Adsorption through Oxygen Vacancies for High‐Performance Lithium‐Carbon Dioxide Batteries

“…For another, the by‐products generated after the decomposition of electrolyte deposited on the electrode to inhibit the following reactions [9] . Even though some catalysts such as Ti 3 C 2 T x MXene applied in the batteries, they still suffer from a relatively high charge potential and obviously incomplete decomposition of Li 2 CO 3 , leading to a relatively poor electrochemical performance [62–64] . However, thanks to the high catalytic activity of O V ‐TiO 2 /MXene in this work, when the charging process was carried out, the generated discharge products would be completely decomposed and the active sites could be exposed to the reactants again in the Li‐CO 2 batteries with O V ‐TiO 2 /MXene electrodes.…”

Synthesis Strategies, Catalytic Applications, and Performance Regulation of Single‐Atom Catalysts

“…batteries. [ 147–153 ] Among them, Li–S batteries (LSBs) with high theoretical energy capacity of 1675 mA h g −1 and abundant resources of S on earth are recognized as one of the most promising choices for advanced energy storage. However, their practical applications are facing pressing challenges such as shuttling of polysulfide, poor electrical conductivity of active S and formed Li 2 S that insoluble damaging to lithium polysulfides (LiPSs) redox.…”

Recent Advances in Lithium–Carbon Dioxide Batteries

“…Hu et al reported an efficient CO 2 catalyst that was prepared by incorporating single Fe atoms into 3D interconnected N‐, S‐doped holey graphene sheets (Figure 9b). [ 95 ] The holey graphene framework could provide sufficient space for up‐taking Li 2 CO 3 discharge products. The whole architecture of the catalyst could facilitate the diffusion of electrons, CO 2 , and Li + ions.…”

“…The whole architecture of the catalyst could facilitate the diffusion of electrons, CO 2 , and Li + ions. [ 95 ] Ti‐based catalysts, CNT‐ or CNF‐supported anatase titania (TiO 2 nanoparticles), have been prepared by our group as the freestanding cathode for Li−CO 2 batteries (Figure 9c). [ 96 ] The authors confirmed the successful reversibility of CO 2 reactions on this easy‐to‐synthesize catalyst.…”

“…Reproduced with permission. [95] Copyright 2020, Wiley-VCH. c) Schematic of the catalytic mechanism of a TiO 2 -NP@CNT/CNF nanocomposite.…”