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. 2020 Jan 7;5(2):1134–1141. doi: 10.1021/acsomega.9b03355

Stable, Dual Redox Unit Organic Electrodes

So Young An †, Tyler B Schon †, Dwight S Seferos †,‡,*
PMCID: PMC6977105  PMID: 31984270

Abstract

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The development of organic materials for electrochemical energy storage has attracted great attention because of their high natural abundance and relatively low toxicity. The bulk of these studies focus on small molecules, polymers, or porous/framework-type materials that employ one type of redox moiety. Here, we report the synthesis and testing of organic materials that incorporate two distinct types of redox units: triptycene-based quinones and perylene diimides. We examine this “dual redox” concept through the synthesis of both frameworks and small molecule model compounds with the redox units positioned at the vertices and connection points. Such a design increases the theoretical capacity of the material. It also imparts high stability because both examples are relatively rigid and highly insoluble in the electrolyte. Lithium-ion batteries consisting of the framework and the small molecule have an excellent cycling retention of 75 and 77%, respectively, over 500 cycles at 1 C. Our work emphasizes the advantages of using multiple redox units in the design of the cathodic materials and redox-active triptycene linkages to achieve high cycling stability.

Introduction

Redox-active organic compounds are promising electrodes for lithium-ion batteries because these compounds have a low mass and the ability to accept multiple electrons, leading to high theoretical capacity.1−6 Small molecules such as carbonyl derivatives are suitable candidates for organic electrodes because of their high specific capacity, widespread abundance, and well-defined redox properties. For example, arylene diimide derivatives such as naphthalene diimides (NDI) and perylene diimides (PDI) are widely used for designing organic electrodes because they are robust industrial dye molecules that have an inherent high stability.7 Quinone derivatives such as benzoquinones and anthracenequinones are promising examples because of their fast and reversible reduction properties, providing high rate capability. Both arylene diimide and quinone derivatives can reversibly accept two electrons at potentials that are appropriated for Li-ion battery operation.

When designing organic materials for battery electrodes, one has to consider their solubility in the electrolyte because dissolution is the most common mechanism of capacity fading. Small molecules tend to readily dissolve in organic electrolytes, causing rapid capacity fading at early discharge/charge cycles.8−13 Higher ordered structures such as polymers14−20 and frameworks21−31 can be prepared as an effective strategy to circumvent this issue. In particular, structures that contain triptycene derivatives32 are intrinsically less soluble in organic solvents and have unique three-dimensional (3D) structure and internal free volume.33−40 Triptycene-based porous materials have been developed and while these electrodes can include redox active groups at linkers and/or vertices (triptycene; core units), most have consisted only one type of redox active group, either at the linker or core units. Such a design inevitably decreases the theoretical capacity because of the presence of redox-inactive mass.41,42 To achieve a higher theoretical capacity, the incorporation of redox-active groups at both the core and the linker is desired.

Here, we present the synthesis and testing of dual redox triptycene-based materials consisting of core building blocks and linkers that are both redox-active (Scheme 1). As discussed above, triptycene derivatives are excellent candidates for a 3D vertex to design core units with low solubility and high stability. PDIs are desirable energy storage materials with reversible redox activity. In this study we have modified triptycene with quinone-type functional groups to provide complementary redox activity for PDI. A framework-type (Fr-PDI) structure and a small molecule system (Sm-PDI) were synthesized, characterized, and tested to determine the generality of this approach.

Scheme 1. Synthetic Route to the Triptycene-Based Fr-PDI and Sm-PDI.

Scheme 1

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Results and Discussion

The synthesis of Fr-PDI begins with triptycene triquinone (Figure S1). Aminated triptycene triquinone (TTQ-NH2) was prepared next by the addition reaction of triptycene triquinone with p-phenylenediamine in ethanol at 0 °C for 12 h. After recrystallization in MeOH, dark-blue colored TTQ-NH2 was obtained in a quantitative yield (89% relative to triptycene triquinone) (Figure S4). The successful synthesis of the resulting product was supported by both the 1H NMR and heteronuclear multiple bond correlation (HMBC) nuclear magnetic resonance (NMR) (Figure S5). The strong coupling between aromatic carbons and protons on phenyl groups is seen in the HMBC NMR spectrum from 7.04–6.62 ppm as expected. Further, the protons on nitrogen atoms from −NH and −NH2 functional groups were identified at 9.26 and 5.26 ppm, respectively. Because these protons are directly attached on the nitrogen atoms, no coupling in the HMBC spectrum was observed in both cases. Interestingly, we observe three different proton peaks at very close chemical shifts in the 1H NMR spectra at 8.50, 8.44, and 8.38 ppm. These protons are presumably because of the existence of regioisomers of TTQ-NH2 products because the addition reaction of p-phenylenediamine is nonregioselective. Note that the synthesized TTQ-NH2 is noticeably less soluble in organic solvents as compared to nonfunctionalized triptycene triquinones. Such a modification not only provides the molecular sites to form the frameworks, but also improves the stability of triptycene triquinone precursors.

Fr-PDI was then prepared by the condensation reaction between TTQ-NH2 and PDI. The Fr-PDIs are dark-red colored powders that are almost completely insoluble in most organic solvents. To characterize these insoluble materials, different techniques such as Fourier-transform infrared spectroscopy (FTIR), solid-state 13C NMR, and high-resolution X-ray photoelectron spectroscopy (XPS) were used. The disappearance of the N–H bands at 3300–3200 cm–1 after the condensation reaction suggests that the amine groups from the aminated framework precursor (TTQ-NH2) were all consumed to form the imide linkages (Figure 1A). The formation of Fr-PDI was further confirmed by the 13C cross-polarization magic-angle-spinning (CP-MAS) NMR (Figure 1B). The presence of the aliphatic carbon peak at ≈40 ppm at the triptycene junction suggests that the triptycene units are still intact after the high temperature condensation reaction. Moreover, the carbonyl peaks at 162 ppm coming from both the core triptycene and PDI, as well as the broad aromatic peaks at 127 ppm provide very strong support for the successful synthesis of Fr-PDI.

Figure 1.

Figure 1

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FTIR spectra of the TTQ-NH2 precursor and Fr-PDI (A), 13C CP-MAS NMR spectrum of Fr-PDI (B), deconvoluted N 1s XPS spectrum of Fr-PDI (C), cyclic voltammogram at a scan rate of 0.5 mV/s (D), galvanostatic discharge/charge curves at current rates of 0.1, 0.3, 0.5, 1, and 3 C (E), and capacity decay and Columbic efficiency at a current rate of 1 C (F) of Fr-PDI in a 1 M LiPF6 ethylene carbonate: dimethoxyethane (1:9 v/v) electrolyte.

To gain additional insight into the formation of Fr-PDI, XPS was used to compare the changes in bonding environments before and after the condensation reaction. Specifically, the N 1s XPS spectra for the precursor TTQ-NH2 contains one nitrogen peak at 400 eV (Figure S6) corresponding to the amine groups. Once formed into Fr-PDI (Figure 1C), the subsequent N 1s spectrum can be deconvoluted into two peaks at 401 and 399 eV, consistent with the new imide linkages and secondary amines present in the starting material.

To test the feasibility of these organic materials as cathodes for lithium-ion batteries, coin cells were assembled with lithium metal as the anode and Fr-PDI as a cathode. Cyclic voltammetry shows that Fr-PDI has one broad reversible peak at 2.5 V versus Li/Li+, that corresponds to the redox-active groups of the triptycene quinones and PDIs (Figure 1D). Such a reversible redox peak resembles the reversible feature of the triptycene triquinone precursor which occurs at 2.6 V versus Li/LI+ (Figure S15C). Figure 1E shows the galvanostatic discharge/charge voltage profiles of Fr-PDI cathode batteries in the range of 1.5–3.5 V at different current densities. Note that the current densities were calculated according to the theoretical capacity of the organic materials where Ctheo = 201 mA h g–1 for Fr-PDI. Overall, one stable discharge plateau was observed in the range of 2.4–2.8 V and the discharge capacity was 93 mA h g–1 for Fr-PDI.

The cycling performance of Fr-PDI was evaluated next. Fr-PDI delivers reversible capacities of 57 mA h g–1 in the first cycle while maintaining around 43 mA h g–1 after 500 cycles at a 1 C rate. Although Fr-PDI displays a slight decrease in capacity upon cycling, this result still demonstrates an 85 and 75% capacity retention after 200 and 500 cycles, respectively (Figure 1F). Moreover, the Columbic efficiency reaches close to 100% during the entire cycling process. Overall, these results suggest that Fr-PDI is a very stable cathodic material because of the high capacity retention rate with an excellent Columbic efficiency.

Inspired by the stability of the Fr-PDI framework, we decided to further evaluate our design at a molecular level. Small molecules with two modified triptycenes connected by one PDI linker were prepared (Scheme 1). The aminated precursor for the small molecule (TMQ-NH2) was prepared from triptycene monoquinone in a similar manner as the previous aminated precursor (Figure S7). The resulting product after the addition reaction of triptycene monoquinone and p-phenylenediamine was purified by column chromatography yielding a dark-green colored powder with 80% yield (relative to triptycene monoquinone). Strong coupling correlations for aromatic protons on the HMBC NMR spectrum were seen at 8.81–7.46 ppm from the triptycene core and 7.05–6.89 ppm from the phenylene linker. Further, the protons on nitrogen atoms were identified at 8.81 and 5.19 ppm for −NH and −NH2, respectively (Figure S8).

Dark-red colored Sm-PDI was obtained after the condensation reaction of TMQ-NH2 and PDI. Different solid-state characterization methods were again utilized to characterize Sm-PDI because this compound has a very low solubility (a requirement for battery operation). First, the formation of Sm-PDI was confirmed by comparing the FTIR spectra of the precursor (TMQ-NH2) and Sm-PDI. The N–H band at 3400–3200 cm–1 disappeared after the condensation reaction, suggesting the complete consumption of the precursor (Figure 2A). CP-MAS NMR provides further support for the successful synthesis of Sm-PDI, showing similar aliphatic carbon peaks, carbonyl peaks, and two different aromatic peaks at 47, 145, 162, and 124 ppm as similarly seen in the Fr-PDI system (Figure 2B). Additionally, the N 1s XPS spectrum of Sm-PDI consists of one peak at 400 eV before the condensation reaction that can be deconvoluted into two peaks at 401 and 399 eV, which further supports the formation of Sm-PDI (Figure 2C).

Figure 2.

Figure 2

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FTIR spectra of the TMQ-NH2 precursor and the Sm-PDI (A), 13C CP-MAS NMR spectrum of Sm-PDI (B), deconvoluted N 1s XPS spectrum of Sm-PDI (C), cyclic voltammogram at a scan rate of 0.5 mV/s (D), galvanostatic discharge/charge curves at a current rates at 0.1, 0.3, 0.5, 1, and 3 C (E), and capacity decay and Columbic efficiency at a current rate 1 C (F) of Sm-PDI in a 1 M LiPF6 ethylene carbonate: dimethoxyethane (1:9 v/v) electrolyte.

Coin cells were assembled using Sm-PDI as the cathode and evaluated by cyclic voltammetry and galvanostatic discharge/charge measurements. Because both Sm-PDI and Fr-PDI consist of the redox active groups of the triptycene quinones and PDIs, their cyclic voltammetry shows the same broad reversible peak at 2.5 V versus Li/Li+ (Figure 2D). Similarly, this redox peak well agrees with the reversible redox peak of the triptycene monoquinone precursor at approximately 2.6 V versus Li/Li+ (Figure S15B). One stable plateau for Sm-PDI was observed with a discharge plateau in the galvanostatic discharge/charge voltage profile in the range of 2.4–2.9 V (Figure 2E). The discharge capacity was 88 mA h g–1 where Ctheo = 141 mA h g–1. Finally, the cycling performance of Sm-PDI was tested. Sm-PDI delivered 88 and 77% capacity retention after 200 and 500 cycles, respectively, with ∼100% Columbic efficiency during cycling (Figure 2F).

It is noteworthy to highlight that Sm-PDI material is a small molecule, which are typically prone to rapid capacity fading, yet this system has a surprisingly high capacity retention and high Columbic efficiency after an extensive cycling. Such a high capacity retention has not been reported in other small molecule NDI/PDI-based Li-ion battery systems (Table 1). Moreover, this value is comparable to the capacity retention of the extremely stable framework and triptycene-based system in the literature.21−24 Overall, both Fr-PDI and Sm-PDI are very stable cathodic materials that can withstand the high cycling process, while maintaining relatively good capacity retention.

Table 1. Comparison of the Studied Fr-PDI and Sm-PDI to Other NDI/PDI-Based Small Molecules and Triptycene-Based Systems for Rechargeable Lithium-Ion Batteriesa.

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a

Abbreviation: n.d., denotes a value not determined; AM, active material; PVdF, poly(vinylidenefluoride); LiClO4, lithium perchlorate; EC, ethylene carbonate; DMC, dimethyl carbonate; LiTFSI, lithium bis(trifluoromethanesulfonyl)imide; DME, dimethoxy ethane; DOL, 1,3-dioxolane; LiNO3, lithium nitrate; LiPF6, lithium hexafluorophosphate.

To gain a further fundamental understanding of our design, we have tested three model compounds that represent fragments of the structures of Fr-PDI and Sm-PDI (Figure S15). The cyclic voltammetry of these compounds agrees with the broad reversible peaks for frameworks and small molecules. More importantly, all of these compounds suffer from poor cycling stability having both the low capacity or low Columbic efficiency after only 20 cycles. It is therefore the combination of these materials demonstrated in our design that yields the higher stability of the framework and the small molecule.

In order to provide more insight into the stability of these organic materials, Fr-PDI and Sm-PDI batteries were disassembled after cell cycling, and their cathodes were recovered. These cathodes were still intact without any delamination after 500 cycles, which confirms their outstanding insolubility in organic solvents (Figure 3, inset). On the other hand, the cathodes consisting of the model compounds were almost completely delaminated after only 25 cycles. (Figure S15 D–F, inset) Considering that Fr-PDI and Sm-PDI are almost completely insoluble in organic electrolytes and the morphology of the active materials are well-distributed in the carbon matrix (Figure 3), the ∼25% decrease in capacity of both systems after 500 cycles could be due to a number of factors including side reactions that chemically degrade the materials after many cycles, geometry changes of the compound during charging and discharging that cause the compound to isolate itself from the conductive carbon network, the partial delamination of the electrode from the current collector and the use of a flexible linker that causes the movement in the molecular structure leading to kinetic barriers such as Li+ charge transfer kinetics over time,41,44 or an overall lack of crystallinity in the electrode materials. In previous studies, we determined that the high crystallinity and smaller aggregate sizes in the electrode could lead to the shorter lithium ion diffusion pathways, a shorter distance that electrons need to travel to reach the entirety of the redox units, and a closer packing of aromatic units which can increase the rate of electron hopping between the redox units, thus leading to high performance of the electrode.45 Both Fr-PDI and Sm-PDI are amorphous and this may have attributed to the overall decrease in capacities.

Figure 3.

Figure 3

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Examination of morphology of Fr-PDI (A) and Sm-PDI (B) using SEM. Inset: Photograph of Fr-PDI (A) and SM-PDI cathodes after cell cycling.

It is common for organic electrodes not to reach their theoretical capacities.18,46−49 Similarly, both of our materials, Fr-PDI and Sm-PDI reach approximately 50% of the corresponding theoretical values at 0.1 C. Possible reasons for this are that the materials have redox units that are electrically isolated because of the nonconjugated structure of the materials, electrostatic repulsion of charged species preventing the multiredox capabilities of the compounds from being realized, or the presence of amines attached to the quinones creating a large overpotential required to attain the desired two electron reduction of the quinones.50,51 One might be able to improve the conductivity of the cathodes by trying different conductive carbon, making nanocomposites or different mechanical mixing techniques such as overhead mixer or ball milling to process.11,52−55 Such techniques allow the organic materials to form smaller aggregate sizes which can help to achieve better stability and high usages of active materials. Nonetheless, the stability of these examples after 500 cycles approaches that of solid-state inorganic cathodes, albeit with lower overall capacity.

In conclusion, we have prepared triptycene-based frameworks and small molecules that contain redox units in both the linker and vertex. Lithium-ion batteries using Fr-PDI delivers a capacity of 93 mA h g–1 at a 0.1 C rate and 75% capacity retention with ∼100% Columbic efficiency after 500 cycles; whereas Sm-PDI delivers a capacity of 88 mA h g–1 and a 77% capacity retention with ∼100% Columbic efficiency after 500 cycles. The stability of the materials is outstanding. It was unexpected that the small molecules would perform as well as the frameworks with an excellent cycling stability. Our strategy not only helps incorporate multiple redox-active functionalities into the design of new materials, but also teaches one how to achieve a high cycling stability, even for a relatively small molecule system. The small molecule example suggests that molecular systems mitigate the necessity to create macromolecular systems that have less well defined structures and should motivate the preparation and testing of these types of structures in the future.

Experimental Methods

Materials Preparation

All reagents were purchased from Sigma-Aldrich and used as received. All electrochemical measurements and construction of lithium-ion batteries were performed at room temperature in an argon-filled glovebox (mBraun) with oxygen and moisture levels below 5 ppm.

Synthesis of Triptycene Tribenzoquinone

The synthesis of tetramethoxy anthracene was based on a procedure previously reported.36 Triptycene tribenzoquinone was prepared as described elsewhere.32 Briefly, a mixture of tetramethoxyanthracene (1.2 g, 4.1 mmol) and 1,4-benzoquinone (2.2 g, 20 mmol) in acetic acid (125 mL) was refluxed for 48 h. The resulting mixture was cooled to room temperature and filtered. The solids were washed with dimethylformamide and acetone to yield red solids. The solids were then dissolved in HI (140 mL) and acetic acid (300 mL) and refluxed for 8 h. The reaction mixture was cooled to room temperature, filtered, and washed with acetone to give grey-colored solids. The resulting solids were stirred with sodium dichromate dihydrate (1.1 g, 3.7 mmol) in acetic acid for 3 h. The reaction mixture was poured into water and neutralized with an aqueous NaHCO3 solution. The solution was then extracted with dichloromethane, and the organic layer was dried over MgSO4 to give 1.2 g of TTQ (86% yield; relative to tetramethoxy anthracene). 1H NMR (CDCl3, 400 MHz) 1H NMR (CDCl3, 400 MHz): δ 6.70 (s, 6H), 6,60 (s, 2H).

Synthesis of TTQ-NH2

p-Phenylenediamine (0.77 g, 7.1 mmol) was added to a solution of TTQ (0.16 g, 0.47 mmol) in EtOH (50 mL). The mixture was stirred at 0 °C for 4 h. The solution was concentrated to dryness and recrystallized in MeOH to give 0.28 g of TTQ-NH2 (89% yield; relative to TTQ). 1H NMR (DMSO, 400 MHz): δ 9.26 (s, 3H), 8.50, 8.44, 8.38 (3H), 7.04–7.02 (m, 6H), 6.64–6.62 (m, 6H), 5.97 (s, 2H), 5.26 (s, 6H).

Synthesis of Fr-PDI

A mixture of TTQ-NH2 (100 mg, 0.15 mmol), zinc acetate (22 mg, 0.12 mmol), perylene-3,4,9,10-tetracarboxylic acid dianhydride (89 mg, 0.22 mmol), and 4.0 g of imidazole was added to a flame-dried 3-necked flask fitted with a reflux condenser. The mixture was backfilled with argon three times to remove any oxygen. The reaction mixture was heated to 160 °C for 24 h. Upon completion, the reaction mixture was cooled to 25 °C and then poured into a stirring solution of methanol. The solid was filtered through a Soxhlet thimble and was extracted with methanol for 1 day and acetone for 3 h. The framework was further purified by dissolving in 15 mL methanesulfonic acid overnight. The solution was then added dropwise to 1 L of methanol in a rapidly stirring beaker. The suspension was then concentrated on a rotary evaporator until the volume of methanol was approximately 500 mL. The suspended frameworks were collected by centrifugation, washed with methanol three times, and dried. (80% yield; relative to TTQ-NH2). 13C CP/MAS NMR: δ 162.11, 127.11, 39.79 ppm.

Synthesis of Triptycene Monoquinone

The synthesis of triptycene monoquinone was based on a procedure previously reported.36 Briefly, a mixture of anthracene (1.2 g, 4.1 mmol) and 1,4-benzoquinone (2.2 g, 20 mmol) in acetic acid (125 mL) was refluxed for 3 h. The resulting mixture was cooled to room temperature and filtered. The crude product was column chromatographed on silica gel using a gradient mixture of hexane and ethyl acetate as the solvent to give 3.0 g of triptycene monoquinone (60% yield; relative to anthracene). 1H NMR (CDCl3, 400 MHz): δ 7.44–7.42 (m, 4H), 7.05–7.03 (m, 4H), 6.60 (s, 2H), 5.80 (s, 2H).

Synthesis of TMQ-NH2

p-Phenylenediamine (0.96 g, 8.9 mmol) was added to a solution of triptycene monoquinone (0.50 g, 1.8 mmol) in tetrahydrofuran (50 mL). The mixture was stirred at 0 °C for 2 h. The solution was concentrated to dryness and column chromatographed on silica gel using a gradient mixture of hexane and ethyl acetate as solvent to give 0.48 g (70% yield; relative to triptycene monoquinone). 1H NMR (DMSO, 400 MHz): δ 8.81 (s, 1H), 7.52–7.46 (m, 4H), 7.05–7.02 (m, 4H), 6.91–6.89 (m, 2H), 6.56–6.54 (m, 2H), 5.86, 5.83 (2H), 5.41 (s, 2H), 5.19 (s, 2H).

Synthesis of Sm-PDI

A mixture of TMQ-NH2 (100 mg, 0.15 mmol), zinc acetate (22 mg, 0.12 mmol), perylene-3,4,9,10-tetracarboxylic acid dianhydride (89 mg, 0.22 mmol), and 4.0 g of imidazole was added to a flame-dried 3-necked flask fitted with a reflux condenser. The mixture was backfilled with argon three times to remove any oxygen. The reaction mixture was heated to 160 °C for 24 h. Upon completion, the reaction mixture was cooled to 25 °C and then poured into a stirring solution of methanol. The solid was filtered through a Soxhlet thimble and was extracted with methanol for 1 day and acetone for 3 h. Sm-PDI was further purified by dissolving in 15 mL methanesulfonic acid overnight. The solution was then added dropwise to 1 L of methanol in a rapidly stirring beaker. The suspension was then concentrated on a rotary evaporator until the volume of methanol was approximately 500 mL. The suspended Sm-PDI were collected by centrifugation, washed with methanol three times, and dried to yield a dark red solid (80% yield; relative to TMQ-NH2). 13C CP/MAS NMR: δ 162.33, 144.93, 124.89, 47.50 ppm.

Synthesis of PDI-An

The synthesis of PDI-An was based on a procedure previously reported.56 A mixture of 3,4,9,10-perylenetetracarboxylicdianhydride (0.5 g, 1.27 mmol), 20 g of imidazole, 50 mg of zinc acetate, and 0.28 mL (3.17 mmol) of aniline was stirred at 100 °C in a two-necked round bottom flask. The temperature of the reaction mixture was increased to 160 °C and maintained at the same temperature for 8 h. The reaction mixture was then cooled to room temperature and acidified with 2 N hydrochloric acid. The precipitate was then filtered and washed with water and dried under vacuum overnight. (83% yield; relative to PDI). 1H NMR (D2SO4, 400 MHz): δ 9.32 (s, 8H), 7.98 (m, 6H), 7.72 (s, 4H).

Coin Cell Assembly

Fr-PDI, Sm-PDI, and the model compounds (PDI-An, TMQ, and TTQ) were ground into a fine powder with a mortar and pestle. The ground organic compounds were then mixed with carbon Super P and PVDF in a 30:60:10 (w/w/w) ratio and suspended in NMP at a concentration 120 mg/mL. The mixtures were then cast on to an aluminum foil using a notch-bar 200 μm. The electrodes were dried in air on a hotplate at a temperature of 80 °C and then in a vacuum antechamber at a temperature of 80 °C before bringing them into the glovebox. CR2023-type coin cells were purchased from MTI Corporation. A copper foil with a diameter of 16 mm (McMaster-Carr) was used as the anodic current collector, a lithium foil with a diameter of 16 mm was used as the reference/auxiliary electrode, and a Celgard polypropylene separator with a diameter of 19 mm was used to prevent short circuiting. An electrode punch (DPM Solution Inc.) was used to cut the electrodes to a 16 mm diameter and a hydraulic press (BT Innovations) was used to hermetically seal the cell. Approximately 80 μL of electrolyte [1:9 (v/v) ethylene carbonate/dimethoxyethane, 1 M LiPF6] was used to fill the cells prior to sealing.

Acknowledgments

This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC), the Canadian Foundation for Innovation, and the Ontario Research Fund. S.Y.A. acknowledges support from NSERC.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.9b03355.

  • Synthetic scheme of triptycene triquinone; 1H NMR studies of tetramethoxyanthracene; 1H NMR of TTQ; synthetic scheme of Fr-PDI; 1H NMR and HMBC NMR spectra of TTQ-NH2; N 1s XPS spectra of TTQ-NH2 and TMQ-NH2; synthetic scheme of Sm-PDI; 1H NMR and HMBC NMR spectra of TMQ-NH2; synthetic scheme of the PDI-An model compound; XPS survey of TTQ, TTQ-NH2, Fr-PDI, TMQ, TMQ-NH2, and Sm-PDI; deconvoluted C 1s XPS spectra of TTQ, TTQ-NH2, Fr-PDI, TMQ, TMQ-NH2, and Sm-PDI; examination of morphology and chemical composition using scanning electron microscopy (SEM) and energy dispersive X-ray; examination of morphology using SEM; electrochemical behavior of TTQ and TMQ; cycling voltammogram and capacity decay and columbic efficiency of PDI-An, TMQ, and TTQ; dQ/dV plot of charge/discharge cycles of Fr-PDI and Sm-PDI; XRD patterns of Fr-PDI and Sm-PDI; and capacity values for Fr-PDI and Sm-PDI(PDF)

This work was supported by the NSERC of Canada, the Canadian Foundation for Innovation, the Ontario Research Fund, and the University of Toronto Connaught Foundation McLean Award. S.Y.A. is an NSERC CGS-D Scholarship Awardee.

The authors declare no competing financial interest.

Supplementary Material

ao9b03355_si_001.pdf (822.9KB, pdf)

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