Stable High‐Capacity Organic Aluminum–Porphyrin Batteries

Abstract

electric vehicles, and more. [4,5] Among these rechargeable battery technologies, sodium, [6][7][8] magnesium, [9,10] zinc, [11,12] calcium, [13] and aluminum [14][15][16] ion batteries have drawn unique attention as the candidates of next-generation batteries. In particular, rechargeable aluminum-ion batteries (AIBs) hold impressive advantages, such as wide temperature range, high safety, and low cost. [17][18][19] However, there is still plenty of room for improving the energy density and long-term life cycle of the positive electrode materials in AIBs. Hence, it is significant to design appropriate positive electrode materials to promote the performance of current AIBs. Recently, extensive efforts have been devoted to the development of organic materials owing to their unique structural features, such as chemical diversity and structure designability, which allows for achieving suitable active molecules for targeted electrodes. [20][21][22] In addition, weak intermolecular forces between active ions in the electrolyte and host materials are beneficial to the reversibility and kinetics of electrochemical reactions. [23,24] Moreover, molecular engineering could be employed to manipulate the voltage plateaus, electrical conductivity, and structural stability of organic materials, which enables the organic molecules to serve as a promising candidate material for next-generation electrode materials.At present, organic electrode materials reported in the AIBs mainly refer to the oxygen or nitrogen active sites in the compounds with carbonyl (CO) or in the nitrogen-containing compounds (CN), due to their structural diversity and chemical stability. In addition, this type of organic material is mainly based on coordination chemical reactions. [21,22,[25][26][27][28] Specifically, many studies on the compounds with carbonyl functional group have been reported. For example, Stoddart [25] and his colleagues synthesized a redox-active phenanthraquinone (PQ) macrocyclic compound, and the corresponding insertion mechanism between aluminum complex ions and conjugated carbonyl materials has been studied. Subsequently, they have improved specific capacity, electrical conductivity, and areal loading via blending PQ with graphite flakes. In the study from Lu and coworkers, [26] a polyimide (PI)/metal-organic framework (MOFs) hybrid material was reported. Also, Wang and coworkers [22] employed PI/CNT as the positive material in Al-organic battery. In the Aluminum-ion batteries (AIBs) attract interest for their promising features of superior safety and long-life energy storage. Organic materials with engineered active groups are considered promising for promoting energy storage capabilities. However, the corresponding energy density (both voltage plateau and sufficient active sites required) and stability are still unexpectedly poor. To address these challenges, here π-conjugated organic porphyrin molecules, that is, 5,10,15,20-tetraphenylporphyrin (H 2 TPP) and 5,10,15,20-tetrakis(4carboxyphenyl) porphyrin (H 2 TCPP), are selec...

Design Strategies of High‐Performance Positive Materials for Nonaqueous Rechargeable Aluminum Batteries: From Crystal Control to Battery Configuration

“…5,10,15,20‐Tetraphenylporphyrin (H 2 TPP) and 5,10,15,20‐tetrakis(4‐carboxyphenyl) porphyrin (H 2 TCPP) were selected to investigate the electrochemical reactions ( Figure a,b). [ 119 ] Porphyrin materials exhibited reversible coordination and dissociation of cationic chloroaluminate (AlCl 2 + ) during discharge and charge processes. Compared with H 2 TCPP, H 2 TPP possessed better electrochemical performance, with a reversible capacity of 101 mAh g –1 at 100 mA g –1 and long‐term cycling stability beyond 5000 cycles at 200 mA g –1 (Figure 8c,d).…”

“…e) HOMO/SOMO/ LUMO plots and correlated energy level diagram of H 2 TPP. f) Two-step redox process of the H 2 TPP electrode obtained by the molecular electrostatic potential method.Reproduced with permission [119]. Copyright 2021, Wiley-VCH.…”

Progress and Trends in Nonaqueous Rechargeable Aluminum Batteries

“…The positive electrodes exhibited superior cyclic stability and capacity. [ 121 ] and the research uncovered that more negative molecular electrostatic potential is beneficial to realize the storage of AlCl 2 + , implying the importance of structural manipulation on organic positive electrodes.…”

“…PANI(H + )@SWCNTs [41] ≈1.0 10 000 ≈110 ≈90 8000 PI/MOFs [44] ≈1.25 1000 73 1800 H 2 TPP [121] ≈1.8 200 84.8 ≈80 5000 tetradiketone [32] 1.3 1000 80 70 8000…”

An Aluminum‐Benzo[1,2‐b:4,5‐b’]dithiophene‐4,8‐dione Organic Rechargeable Battery Featuring Low Self‐Discharge

“…The cell was cycled for 5 cycles at 20 mA g À 1 prior [25,56] f) Average discharge capacity vs. diffusive cell-level capacity of the previously reported cathode materials. [25,38,50,[57][58][59] Purple squares: AlCl 4 À intercalation type electrodes. Orange squares and star: AlCl 2 + intercalation type electrodes.…”