High Rate and Long Lifespan Sodium-Organic Batteries Using Pseudocapacitive Porphyrin Complexes-Based Cathode

Abstract

Highlights Functionalized porphyrin complexes are proposed as new pseudocapacitive cathodes for SIBs based on four-electron transfer. The presence of copper(II) ion partially contributes the charge storage and significantly stabilizes the structure of porphyrin complex for electrochemical energy storage. The electrochemical polymerization of porphyrin complex through the ethynyl groups in self-stabilization process contributes to high rate capability and excellent cycling stability. Abstract Sodium-organic batteries utilizing natural abundance of sodium element and renewable active materials gain great attentions for grid-scale applications. However, the development is still limited by lack of suitable organic cathode materials with high electronic conductivity that can be operated stably in liquid electrolyte. Herein, we present 5,15-bis(ethynyl)-10,20-diphenylporphyrin (DEPP) and [5,15-bis(ethynyl)-10,20-diphenylporphinato]copper(II) (CuDEPP) as new cathodes for extremely stable sodium-organic batteries. The copper(II) ion partially contributes the charge storage and significantly stabilizes the structure of porphyrin complex for electrochemical energy storage. In situ electrochemical stabilization of organic cathode with a lower charging current density was identified which enables both improved high energy density and power density. An excellent long-term cycling stability up to 600 cycles and an extremely high power density of 28 kW kg −1 were achieved for porphyrin-based cathode. This observation would open new pathway for developing highly stable sodium-organic cathode for electrochemical energy storage. Supplementary Information The online version of this article (10.1007/s40820-021-00593-8) contains supplementary material, which is available to authorized users.

Ethynyl and Furyl Functionalized Porphyrin Complexes as New Organic Cathodes Enabling High Power Density and Long-Term Cycling Stability

“…Hence, organic cathode materials have recently attracted abundant attention and various organic cathode materials were gradually reported in the electrochemical energy-storage (EES) systems. For example, quinones, − phthalocyanines, − porphyrins, − conductive polymers, − organosulfur compounds, − etc. were continuously utilized in the rechargeable organic lithium-based batteries (ROLBs).…”

Ionothermal Synthesis of Fully Conjugated Covalent Organic Frameworks for High‐Capacity and Ultrastable Potassium‐Ion Batteries

“…Before discharge, the N 1s spectra can be resolved into three peaks due to Zn‐N (398.8 eV), CN (399.1 eV), and CN (399.6 eV). [ 58,59 ] Obviously, along with the potassiation process, the CN peak intensity gets increased, while the one due to CN gets decreased, and with the emergence of K + N peaks, indicating the formation of CNK group via the interaction between K + and CN during the potassiation process. After depotassiation, the intensity of the CN peak gets decreased, while the CN peak intensity gets increased, and the K + N peaks disappeared, disclosing the reversible interaction between K + and the CN groups in QPP‐FAC‐Pc‐COF, consistent with the C 1s XPS spectroscopic result as detailed above and further confirming the reaction occurring between CN and K + .…”

Cuprous Chloride as a New Cathode Material for Room Temperature Chloride Ion Batteries

“…Lithium-ion batteries (LIBs) have fulfilled nowadays energy storage needs in consumer electronics, electric vehicles and grid storage. [1][2][3][4][5][6] Apart from the development of LIBs, postlithium battery based on cation shuttling were also proposed, such as K + , Na + , Al 3 + , and Mg 2 + . [7][8][9][10][11][12][13][14][15] These batteries showed promising advantages in terms of the cost and safety, although the energy density was still relatively low compared to the lithium ion battery.…”

“…Lithium‐ion batteries (LIBs) have fulfilled nowadays energy storage needs in consumer electronics, electric vehicles and grid storage [1–6] . Apart from the development of LIBs, post‐lithium battery based on cation shuttling were also proposed, such as K + , Na + , Al 3+ , and Mg 2+ [7–15] .…”