A Porphyrin Complex as a Self‐Conditioned Electrode Material for High‐Performance Energy Storage

Abstract

The novel functionalizedp orphyrin [5,15-bis-(ethynyl)-10,20-diphenylporphinato]copper(II) (CuDEPP) was used as electrodes for rechargeable energy-storage systems with an extraordinary combination of storage capacity,r ate capability,a nd cycling stability.T he ability of CuDEPP to serve as an electron donor or acceptor supports various energystorage applications.C ombined with al ithium negative electrode,t he CuDEPP electrode exhibited al ong cycle life of several thousand cycles and fast charge-discharge rates up to 53 Cand aspecific energy density of 345 Wh kg À1 at aspecific power density of 29 kW kg À1 .Coupled with agraphite cathode, the CuDEPP anode delivered as pecific power density of 14 kW kg À1 .W hereas the capacity is in the range of that of ordinary lithium-ion batteries,t he CuDEPP electrode has ap ower density in the range of that of supercapacitors,t hus opening ap athway toward new organic electrodes with excellent rate capability and cyclic stability.Long-term success in electric mobility and grid-scale energy storage requires electrochemical energy-storage (EES) systems with high energy,h igh power, long cycle life,r eliable safety,a nd low cost. [1][2][3] Conventional lithium-ion batteries (LIBs) based on inorganic materials possess the highest energy density among the current EES systems,b ut have al ow power output because of the slow charge/discharge kinetics. [4,5] In contrast, electrochemical capacitors (ECs) are known as high-power EES systems;however, they exhibit low energy densities owing to the limited surface charge-storage capabilities. [6][7][8] Furthermore,t he use of transition-metalbased electrode materials raises critical concerns regarding the depletion of resources as well as expensive and environmentally unfriendly production. [9] Theaffordability and innocuous and biologically friendly nature of organic materials make them both environmentally and economically attractive.C onsiderable effort has been devoted to the development of organic electrodes for rechargeable batteries,r edox-flow batteries,a nd supercapacitors. [10][11][12][13][14][15][16] However,t he present organic electrode materials suffer from low electrical conductivity and dissolution into the electrolyte. [13,14] Accordingly,t he improvement of rate capability and cyclability is the major challenge for research on organic electrodes.Porphyrins are ubiquitous in nature and perform essential functions of life. [17] Thea ttractive electronic emission and absorption properties of porphyrin compounds have been investigated for light harvesting and catalytic applications. [18][19][20] Shin et al. initally reported the use of anorcorrole nickel(II) complex as an electrode material in batteries,t he mechanism for which was proposed on the basis of the transformation from antiaromatic to aromatic states of the porphyrin. [16] In fact, 16p and 20p porphyrins,p roduced by oxidizing or reducing the 18p porphyrins,have been successfully isolated, [21][22][23] thus suggesting that porphyrins might serve as bipolar orga...

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

“…The CuDEPP crystalizes in triclinic system with space group [ 30 ], and the packing structure of CuDEPP shows that the porphyrin rings stack parallel with offset center that Cu sits between the C≡C triple bonds of the neighboring porphyrins. In order to gain more insight into the evolution of the CuDEPP crystal structure upon sodium-ion storage, in situ XRD characterization on CuDEPP electrode during the first cycle was monitored (Fig.…”

“…Considering the solubility of porphyrins in organic electrolytes, developing functionalized porphyrins with different organic groups and their polymers is an effective strategy for designing stable electrodes, which is a precondition for ensuring a long lifespan in sodium-organic battery. It was reported that the [5,15-bis-(ethynyl)-10,20-diphenylporphinato]copper(II) (CuDEPP) became less soluble and extremely stable through chemical functionalization of introducing an ethynyl group at the meso-position of porphyrin complex [5,10,15,20-tetraphenylporphinato]copper(II) (CuTPP) [ 30 ]. The improved stability of porphyrins in common solvents was owing to the enhanced intermolecular π-cation interaction and the self-polymerization process during the initial charge–discharge processes.…”

A bipolar metal phthalocyanine complex for sodium dual-ion battery

“…And Tables S1 /Na + . Compared with the first anion/cation, the binding of the second anion/cation shows stronger binding energy, indicating the feasibility of the binding between CuTAPc with two anion/cation to generate the fourelectron reaction [37,38,46].…”

“…Moreover, organic electrode materials are recognized as the promising candidate due to their low cost, resource sustainability, and structural diversity [29][30][31][32][33][34][35]. Most importantly, the molecular level controllability could endow the organic compounds with bipolar feature [36][37][38][39], which could interact with both cations and anions, respectively, thereby offering the possibility to construct organic material-based SDIBs. However, to our knowledge, there is no reports about bipolar organic material-based SDIBs.…”

Supercapacitor electrodes based on metal‐organic compounds from the first transition metal series

“…So far, reported copper‐organic compounds and their composites with SC properties can be divided into copper carboxylate MOFs ( 140 ‐ 157 ), copper polyoxometalate organic frameworks (Cu‐POMOFs, 158 ‐ 176 ), copper polyamine or polyphenol MOFs ( 177 ‐ 183 ), copper porphyrin compounds ( 184 ‐ 188 ), etc. Copper can exhibit electrochemical activity through the redox reaction between Cu(0), Cu(I), and Cu(II), and its organic compounds have been widely studied in SCs 73,77,78,80,116,159‐183 . Relevant conversion process can be expressed by the following equations 164,167,174 : …”