Perylene-polyimide-Based Organic Electrode Materials for Rechargeable Lithium Batteries

Abstract

Organic materials for Li-ion battery application continue gaining attention due the virtue of low cost, environmental benignity, and so on. A new class of electroactive organic material called polyimides is particularly important due to the extra stability exhibited at higher current rates. High-performance rechargeable lithium battery cathodes based on polyimides of 3,4,9,10-perylenetetracarboxylicacid-dianhydride are prepared. The novel electrodes exhibit good rate capability and improved cycling stability, which result from their combined beneficial properties such as the presence of additional carbonyl groups, favorable band gap, and enhanced conductivity, making it a potential material for greener and sustainable electrochemical storage devices. SECTION: Energy Conversion and Storage; Energy and Charge Transport S torage and utilization of sustainable energy via an environmentally friendly route is an important aspect of energy economy. 1−3 With a growing need for clean and efficient energy-storage technologies, rechargeable Li-ion batteries are undoubtedly the state-of-the-art and hence continue to gain both scientific and commercial importance for their applications in portable electronics and vehicular sector. 4−6 However, designing advanced batteries that are highly energy efficient and eco-friendly is still a major challenge. The current Li-ion battery technology with active inorganic insertion electrode materials such as LiCoO 2 fails to fulfill the demand in terms of safety and sustainability. Recently, there has been wide interest toward developing "greener and sustainable" rechargeable lithium batteries based on organic electrode-active materials. 7−10 Research on organic electrodes for rechargeable lithium batteries, although started several years back, did not gain much importance until recently, partially due to their poor performances and wide acceptance of transitional-metal-based inorganic electrodes. Transition from inorganic to organic material-based electrodes could be a possible alternative, and several groups have turned toward "organic approach", thanks to the rich and versatile chemistry available for organic synthesis that allows the design of electrode materials with high level of control over the functionalities and tunable redox properties without the use of heavy metals and hightemperature synthesis. 1 In recent years, several redox-active organic materials such as organosulphur, 11 radical polymers, 12,13 and carbonyl 14 -based compounds have been studied as electrodes for Li-based batteries and were reported to exhibit reversible reactivity with Li. However, the performance characteristics of such organic electrodes for their application in Li-ion battery were limited due to several factors such as electrode dissolution, thermal instability, and so on. Reversible redox properties of carbonyl-based organic molecules have been extensively studied by several groups. 1,10,14−16 Nevertheless, organic-based materials present some drawbacks such as low thermal stability, low conductivit...

A polyimide based all-organic sodium ion battery

“…The shifts in the carbonyl stretching frequencies suggest the conversion of anhydride functionality to imide functionality and the values match with previous report. 23 Phase purity of PI is confirmed from a comparison with the powder XRD patterns of PI-IMI reported earlier (Fig. 1b).…”

Molecular Design Strategies for Electrochemical Behavior of Aromatic Carbonyl Compounds in Organic and Aqueous Electrolytes

“…Polymerization could effectively alleviate the solubility by ensuring that the average relative molecular mass was constant while increasing the total relative molecular mass. [105] Polymers with three different π-conjugated structures exhibited relatively good electrochemical properties. [103] This part summarizes the molecular structure modifications and discusses effective measures for improving the inherent insulation, such as the use of mixed carbon materials.…”

“…The substitution of alkyl and benzene rings can indirectly change the electron cloud density of carbonyl groups, and R structures with active carbonyl groups can increase the number of carbonyl groups participating in the reaction. [105] PI-10 exhibited an enhancement in the reduction potential to 2.15 V caused by the introduction of an S heteroatom and delivered a high specific www.advancedsciencenews.com capacity of 160 mAh g −1 and a long cycling stability, with 120 mAh g −1 after 450 cycles at 1.5 C. [110] The benefit of the active sites was that they could increase the capacity, decrease the LUMO energy, and improve the electronic affinity of the molecules. [108] PI-13 displayed a C initial of 130 mAh g −1 and 94.7% capacity after 50 cycles at 1 C. [105] The influence of substituents on the electrochemical properties was studied.…”

Molecular Engineering with Organic Carbonyl Electrode Materials for Advanced Stationary and Redox Flow Rechargeable Batteries

“…[86] Unlike pristine PTCDA, which can only realize electron transfer through π-π stacking between the layers, thioether bonds can induce π-electron delocalization between the perylene rings and thus provide an additional electron conduction pathway. [132][133][134][135][136][137] In 2010, Zhan's group first reported a series of polyimides (8-14, 15, 8-17 to 8-19) as cathode materials for LIBs. Through an activation process, no obvious capacity (≈140 mAh g -1 ) fading was observed after more than 250 cycles at a current density of 100 mA g -1 .…”

“…The superior electrode performance motivated researchers to further study this intriguing class of PIs(8-16, 8-20 to 8-24) [119,133,138,139]. The superior electrode performance motivated researchers to further study this intriguing class of PIs(8-16, 8-20 to 8-24) [119,133,138,139].…”