Fast‐Charging and Durable Organic Cathodes Enabled by Two‐Dimensional Supramolecular Polymerization

ABSTRACT

Strong demand for fast‐charging and durable batteries drives research into high‐performance organic electrodes beyond conventional layered metal oxides. However, small‐molecule organic electrode materials suffer from sluggish ion diffusion and high dissolution in electrolytes, limiting their practical applications. Here we present sulfur‐heterocyclic extension of redox‐active triptycene tribenzoquinone monomers, enabling two‐dimensional supramolecular polymerization to yield porous multilayer nanosheets with architectural robustness. This supramolecular engineering achieves rapid and stable lithium (Li) storage through cross‐flow ion transport dominated by pseudocapacitance. At a current density of 18 A g⁻¹, a power‐densed organic cathode (∼42 kW kg⁻¹) reaches 76% state‐of‐charge (SoC) only in 44 seconds while retaining 79% of its capacity over 5,000 cycles. Its superior high‐rate performance and cycling stability persist even under cryogenic conditions. We demonstrate its practicability with a Li–organic pouch cell featuring a high areal capacity of 5 mAh cm⁻² and 6C‐charging capability to 66% SoC, which fully meets the performance metrics of practical fast‐charging Li‐ion batteries.

Sulfur‐heterocyclic extension strategy of triptycene tribenzoquinone enables a 2D supramolecular polymer cathode with cross‐flow fast Li storage. This work achieves 76% state of charge in 44 s, 79% capacity retention over 5,000 cycles, and a practical Li–organic pouch cell for fast charging at 6C.

1. Introduction

Recent surge in energy storage devices used for portable electronics and electric vehicles has placed ever‐growing demands on rechargeable batteries, preferably with high energy and power densities, long lifespan, high safety, and low costs [1, 2, 3]. Lithium (Li)‐ion batteries (LIBs) based on layered metal oxides as energy‐densed cathode materials have garnered much attention [4, 5, 6, 7]. However, such strong demands for commercial LIBs inevitably give rise to a heavy consumption of the limited transition metal resources, bringing about high production costs and potential environmental concerns [8, 9].

Organic cathode materials have been promising candidates for sustainable energy storage due to the composition of abundant light elements (e.g. carbon, hydrogen, oxygen, nitrogen, sulfur, etc.) [10, 11, 12, 13]. Their chemical structures can be molecularly tailored to realize electrochemical reactions with Li and other earth‐abundant metal ions such as sodium [14, 15, 16], calcium [17, 18], and zinc [19, 20, 21]. Among these, n‐type redox‐active carbonyl (C═O) compounds, including quinone derivatives [22, 23, 24], carboxylate salts [25], anhydrides [26], and imides [27], have been extensively studied owing to their high energy storage capabilities and rapid enolization kinetics. Research on carbonyl‐based organic cathode materials originated with the discovery of electrochemical activity in dichloroisocyanuric acid in 1969 [28] and experienced a revival in 2008 when Tarascon and coworkers reported dilithium rhodizonate [29]. Over the past decades, numerous carbonyl small molecules have been synthesized to pursue high capacity [30, 31, 32]. However, their intrinsically insulating nature and high solubility in aprotic electrolytes impair the power capability and cause capacity fade [33, 34]. For instance, multi‐electron electroactive triptycene tribenzoquinone (TTQ), when used as an organic cathode, delivers high capacity and energy density exceeding 1000 Wh kg⁻¹, yet exhibits poor cycling stability owing to its high solubility in ether‐based electrolytes [32]. This dissolution challenge has been well addressed through various chemical strategies, including covalent [35, 36, 37, 38] and noncovalent polymerization [22, 39, 40], salification [41], and modification with conductive carbons [42]. Very recently, a carbonyl‐based n‐type conducting polymer has succeeded in practical organic batteries owing to its excellent mixed ionic and electronic transport and low solubility [43]. While the cycling lifespans of n‐type organic batteries have been significantly prolonged [44, 45], their rate capability lags far behind the ultrafast‐charging requirement. Conversely, although some p‐type polymers have achieved a 100C‐charging rate for anion chemistry in organic cathodes [46], their much lower capacities relative to n‐type counterparts impose a penalty on the energy density of organic batteries.

The sluggish ion transport kinetics in electrodes is recognized as one of the bottlenecks to fast charging [47]. Theoretically, an ideal electrode structure for fast charging requires three‐dimensional (3D) interpenetrating ion‐diffusion pathways with the shortest distance [48, 49, 50]. Although the concept of 3D battery architecture has been proposed for decades [51], controlling the pore network tortuosity of electrodes to substantially boost ion flows remains challenging [52]. Recently, we proposed a rational design principle for two‐dimensional (2D) polymer cathodes to enable ultrafast charging of Li–organic batteries [53]. A key to this achievement was the construction of cross‐flow shortcuts for Li⁺ transport via synergistic intercalation and penetration.

Inheriting the cross‐flow structural design, we molecularly reform shape‐persistent TTQ derivatives via heterocyclic extension, serving as redox‐active cathode materials in fast‐charging and durable Li–organic batteries. This architectural tailoring serves two purposes (Figure 1a): i) enhancing intermolecular interactions between dimeric blades to confine supramolecular polymerization in 2D [54, 55, 56], thereby significantly suppressing dissolution in electrolytes, and ii) introducing more carbonyl groups to improve energy density. A desired 2D supramolecular polymer with intralayer nanopores is anticipated to facilitate cross‐flow Li⁺ transport (Figure 1b). This, together with surface‐controlled pseudocapacitance, holistically boosts the electrochemical performance of organic batteries (Figure 1c). At a high current density of 18 A g⁻¹, the heterocycle‐extended TTQ cathode achieves 76% state‐of‐charge (SoC) in 44 s and shows 79% capacity retention after 5,000 cycles. Furthermore, we successfully demonstrate its practicability by assembling a Li–organic pouch cell with high areal capacity and fast‐charging capability.

FIGURE 1.

Design and simulation of heterocyclic TTQ cathode materials. (a) Schematic of the molecular extension of TTQ. (b) Possible models depicting a 2D supramolecular polymer of the heterocyclic TTQ, highlighting intralayer pores and structural defects. (c) Comprehensive comparison of the electrochemical performance of heterocyclic TTQs in this work with TTQ cathode materials. (d and e) Molecular structures of STTQ‐1 (d, left), STTQ‐2 (d, right), and OTTQ (e) monomers. (Inset) Li‐storage mechanism of carbonyl groups in a quinonoid motif. (f) Optimized configurations of STTQ‐1, STTQ‐2, and OTTQ dimers with the visualized noncovalent interactions. Green regions indicate iso‐surfaces where van der Waals interaction exists. Gray, red, yellow, white bars represent carbon, oxygen, sulfur, and hydrogen atoms.

2. Results and Discussion

2.1. Materials Design and Synthesis

In the previous work [53], we covalently polymerized TTQ monomers via dithioether heterocycles to enhance cycling durability of organic batteries. We envisage that rigid TTQ‐based building blocks, when carrying three longer blades, spontaneously adopt a 2D lamellar arrangement [57, 58]. Analogous to triptycene‐based 2D polymers [53, 59], the resulting supramolecular polymers would exhibit weak interlayer van der Waals interactions instead of π–π stacking [59]. Coupled with abundant intralayer nanopores, this supramolecular engineering creates cross‐flow channels facilitating Li⁺ transport (Figure 1b). As a proof of concept, we synthesized two propeller‐shaped TTQ monomers STTQ‐1 and STTQ‐2, with sulfur‐heterocycle‐extended blades of varying lengths (Figure 1d). To further investigate the role of sulfur heterocycles in electrochemical performance, we also prepared an oxygen‐heterocyclic TTQ monomer OTTQ as reference (Figure 1e). Density functional theory (DFT) simulation indicated that the heterocycle‐extended blades prefer to stack in a dimeric, antiparallel fashion via noncovalent interactions (Figure 1f), thereby possibly resulting in a quasi‐hexagonal, nanoporous 2D assembly (Figure 1b). Notably, STTQ‐1 possesses a theoretical energy density up to 820 Wh kg⁻¹, higher than that of other two counterparts.

2.2. Structural Characterization

We first identified the chemical structures of the as‐prepared heterocyclic TTQ monomers through spectroscopies. High‐resolution mass spectrometry preliminarily detected molecular ion peaks of the target compounds (Figure S1). Fourier transform infrared (FTIR) spectra of STTQs displayed distinct vibrational stretches attributed to C═O, unsaturated carbon (C═C), and thioether (C−S−C) groups (Figure 2a), confirming the presence of quinonoid units and dithioether heterocycles. Furthermore, solid‐state ¹³C cross‐polarization magic angle spinning (CP‐MAS) nuclear magnetic resonance (NMR) spectroscopy validated the definite chemical states of carbon atoms in C═O, C−S−C, C = C, and C−H bonds (Figure 2b). Likewise, x‐ray photoelectron spectroscopy (XPS; Figure S2) indicated that all oxygen and sulfur atoms in STTQs existed as C═O and C−S−C bonds, respectively (Figure 2c). In contrast, OTTQ showed signals corresponding to ether (C−O−C) groups based on oxygens (Figure 2a–c).

FIGURE 2.

Structural characterization of heterocyclic TTQs. (a) Partial FTIR spectra at 25°C, with assignment of functional groups. (b) Solid‐state ¹³C CP‐MAS NMR spectra at 25°C, with assignment of carbons. (c) High‐resolution O 1s and S 2p XPS spectra at 25°C. (d) Reflection‐mode OM image of STTQ‐1. Scale bar, 50 µm. (e) False‐colored SEM image and corresponding EDX elemental mapping of STTQ‐1. Scale bars, 20 µm. (f) False‐colored zoom‐in SEM image in (e) of a thicker fragment of STTQ‐1 from cross‐sectional view. Scale bar, 1 µm. (g) Tapping‐mode AFM image and height profile of multilayer nanosheets of STTQ‐1. Scale bar, 5 µm. (h) High‐resolution AFM phase and fast Fourier transform (FFT, inset) images of a monolayer nanosheet of STTQ‐1. Scale bar, 2 nm. (i) AFM (upper)‐IR (bottom) mapping at 1650 cm⁻¹ for nanosheets of STTQ‐1. Scale bars, 1 µm. The microscopic characterization of the drop‐casted samples was measured on silicon.

Thermogravimetric analysis revealed that the heterocyclic TTQ monomers began to decompose gradually at ∼270°C but retained >60 wt% mass at 700°C (Figure S3), indicating high thermal stability. Unexpectedly, however, powder x‐ray diffraction (Figure S4) revealed the lack of long‐range in‐plane ordering in any heterocyclic TTQs for the intended 2D honeycomb polymers. To evaluate their porosity, we measured CO₂ adsorption isotherms at low pressures and 0°C (Figure S5a–c). Pore‐size distribution analysis via DFT confirmed the presence of micropores within the resulting supramolecular materials (Figure S5d–f).

Next, we characterized supramolecular structures formed by the heterocyclic TTQs using various microscopies. Their stable dispersions in N,N‐dimethylformamide (DMF) displayed strong Tyndall light scattering (Figure S6). Figure 2d–i shows representative images of STTQ‐1 dispersion drop‐casted on different substrates. Reflection‐mode optical microscopy (OM) revealed several irregular sheet‐like fragments with optically flat surfaces (Figure 2d), implying the formation of 2D supramolecular polymers. Scanning electron microscopy (SEM) demonstrated that a thicker fragment adopts compact laminar structures (Figure 2e,f). Elemental mapping via energy‐dispersive x‐ray (EDX) spectroscopy showed uniform distributions of carbon, oxygen, and sulfur within the fragment (Figure 2e). Analogous sheet‐like morphology was observed in the exfoliated nanosheets obtained by ultrasonication (Figure S7). Consistent with these observations, a tapping‐mode atomic force microscopy (AFM) image clearly illustrated that these exfoliated nanosheets exhibit multilayer‐stacked 2D features, typically with micrometer‐scale lateral dimensions and an average thickness of ∼4 nm (Figure 2g). The thinnest nanosheets were measured for less than 1‐nm thick, in agreement with the monolayered model of self‐assembled STTQ‐1 (Figure S8). High‐resolution AFM further demonstrated that STTQ‐1 adopts a quasi‐hexagonal order in short range (Figure 2h). To elucidate the vertical configuration of STTQ‐1, we investigated molecular orientation in its nanosheets via AFM‐IR microscopy. As shown in Figure 2i, the stretching vibrations of C═O bonds were distinctly probed within the 2D framework (Figure S9), confirming the perpendicular alignment of all quinone units. Similarly, STTQ‐2 (Figure S10) and OTTQ (Figure S11) exhibit characteristic 2D morphology when characterized using the same methods.

2.3. Electrochemical Performance

We assembled coin‐type cells with Li‐metal anodes to evaluate the electrochemical performance of the heterocyclic TTQs as cathode active materials. These materials showed negligible dissolution in ether‐based electrolytes (Figure S12). Ester‐based electrolytes, however, were avoided as they were found to impair the battery performance (Figure S13) via side reactions with the quinone‐based organic electrodes [60]. In the cyclic voltammetry (CV) profiles, the STTQ‐1 cathode (Figure S14a) displayed four overlapped redox pairs at 3.01/3.04, 2.62/2.70, 2.41/2.52, and 2.00/2.08 V versus Li/Li⁺, while the STTQ‐2 cathode exhibited two sharp redox peaks at 2.65/3.02 and 2.22/2.41 V versus Li/Li⁺ (Figure S14b). In contrast, OTTQ possessed a broad redox pair at 2.80/2.84 V versus Li/Li⁺ (Figure S14c). Consistent with CV curves, their galvanostatic charge/discharge profiles displayed sloping plateaus with an average potential ranging from 2.40 V to 2.55 V versus Li/Li⁺ (Figure 3a). At a low current density of 60 mA g⁻¹, the STTQ‐1 and STTQ‐2 cathodes delivered high specific capacities of 288 and 239 mAh g⁻¹, respectively (Figure 3a), whereas the OTTQ cathode showed a substantially lower capacity of 135 mAh g⁻¹ (Figure 3a). These values are deemed as 100% SoC given that organic electrode materials rarely achieve their theoretical capacities [44]. Moreover, the STTQ cathodes self‐discharged within only 5% for 24 h (Figure S15).

FIGURE 3.

Electrochemical performance of heterocyclic TTQ cathodes. (a) Galvanostatic charge/discharge profiles in a potential window of 1.5−3.5 V vs. Li/Li⁺ at a current density of 0.06 A g⁻¹. (b) Charge (circles) and discharge (dots) capacities at 25°C and at charge rates of 0.3C−60C. (c) Ragone plot of gravimetric energy density versus power density with charging time (dashed lines) of heterocyclic TTQs and benchmarked cathode materials. (d) Long‐term cycling (dots) and coulombic efficiency (circles) at a current density of 4.5 A g⁻¹. (e) Comparison of capacity retention versus cycle number of heterocyclic TTQs (full lines) with reported cathode materials. (f) Charge (circles) and discharge (dots) capacities at a current density of 0.15 A g⁻¹ from 25°C to −40°C. (g) Charge (circles) and discharge (dots) capacities at −25°C and at charge rates of 0.3C−5C. (h) Cycling performance at −25°C and at a current density of 0.3 A g⁻¹.

Beyond high specific capacities, STTQ cathodes perform fast charging and high‐power output. As shown in Figure 3b, STTQ‐1 delivered a specific capacity of 243 mAh g⁻¹ at a high rate of 15C (1C is equal to 0.3 A g⁻¹), achieving 84% SoC within 4 min. Even at 60C, it maintained a stable capacity of 220 mAh g⁻¹ and still recovered the full state at 0.3C (Figure 3b). This outstanding rate capability yielded a specific power up to 42 kW kg⁻¹ (Figure 3c), enabling charging to 76% SoC in 44 s (Figure S16a). While STTQ‐2 achieved higher SoC more rapidly during charging (Figure 3b), its specific energy density was relatively lower (Figure S16b). In sharp contrast, the OTTQ cathode reached only 51% SoC at 60C (Figure S16c), underperforming both STTQ derivatives. When benchmarked against other cathode material classes (Figure S17 and Tables S1–S3), STTQs exhibit rate performance that ranks among the best, rivalling a 2D polymer cathode developed recently (^2DVLP; Figure 3c) and superior to the structurally unmodified TTQ (Figure S18).

Cycling performance is equally important for practical cathode materials. As shown in Figure 3d, all heterocyclic TTQ cathodes showed capacity retention exceeding 70% for 5,000 cycles at 15C (Figure S19) and even 30C (Figure S20), significantly surpassing the TTQ (<1000 cycles). Remarkably, both STTQ‐1 and OTTQ operated with 80% capacity retention over 4,500 cycles (Figure 3e). Their lifespans exceed the most reported cathode materials (Figure S17 and Tables S1–S3), notably the aforementioned 2D polymer cathode (Figure 3e). In contrast, we observed a moderate decay on the specific capacity of STTQ‐2, which remained 71% after 5,000 cycles (Figure 3d). Accordingly, STTQ‐2 operated for over 2,500 cycles (Figure 3e). Post‐cycling SEM analysis confirmed well preservation of sheet‐like nanostructures in the STTQ cathodes (Figure S21). While dendritic Li metal was rarely detected on the anodes of both STTQ‐based organic cells, the STTQ‐1‐based cell exhibited a smoother anode surface than its STTQ‐2 counterpart (Figure S22). Elastic modulus analysis of the STTQ nanosheets revealed a distinct difference in their inherent mechanical properties (Figure S23), possibly affecting the structural stability during cycling.

We further explored low‐temperature performance of STTQ cathodes. As the ambient temperature dropped to −40°C, STTQ‐1 underwent a gradual capacity decline from 269 to 189 mAh g⁻¹ (Figure S24a) to retain over 70% capacity (Figure 3f), outperforming other reported cathodes (Table S4). Similarly, STTQ‐2 showed 71% capacity retention at −40°C (Figure 3f), though with lower overall specific capacity (Figure S24b). Notably, the fast‐charging capability of both two STTQ cathodes was demonstrated under cryogenic conditions. At −25°C and 5C, STTQ‐1 retained a capacity of 146 mAh g⁻¹ (Figure S25a), corresponding to 51% SoC (Figure 3g), while STTQ‐2 exhibited comparable rate capability but delivered a lower capacity of 119 mAh g⁻¹ (Figures 3g and S25b). However, a distinct decline in rate performance was observed when the environmental temperature further dropped to −40°C (Figure S26). Nevertheless, both electrodes enabled stable cycling at −25°C, affording >80% capacity retention after 600 cycles (Figures 3h and S27).

2.4. Li⁺ Storage and Transport Behavior

To elucidate Li⁺ transport kinetics in the heterocyclic TTQ cathodes, we first identified Li storage sites using ex situ FTIR spectroscopy and XPS analysis. As expected, the characteristic peak assignable to the C═O group progressively diminished when cathodes were discharged to 1.5 V and reversibly reappeared upon recharging to 3.5 V (Figure S28). Consistently, high‐resolution O 1s XPS spectra revealed analogous reversible switching between C═O and C–O states (Figure S29a–c). In contrast, we did not observe any variation of the S 2p (Figure S29d,e) and accordingly ruled out a high‐potential p‐type redox reaction triggered by the C−S−C group associated with counter anions [61, 62]. These results confirm that reversible charge storage occurs only through the reversible enolization of C═O groups (Figure 1d, inset), analogue to other quinone‐based organic electrodes [53, 63]. DFT calculation corroborated the Li storage mechanism described above. Electrostatic potential (ESP) mapping on heterocyclic TTQs (Figure 4a) revealed that the C═O groups together with adjacent heteroatoms constitute the active region to coordinate with Li⁺. From the redox energy landscape for multiple lithiation processes (Figure S30), we confirmed that the C═O groups in heterocyclic TTQs serve as redox‐active sites for storing Li⁺. Using in situ electrochemical impedance spectroscopy (EIS; Figure S31), we tracked the evolution of the charge‐transfer resistance (R _ct) during the first charge/discharge cycle, which exhibited a reversible rise and fall. This, together with the calculated lithiation processes (Figure S30), means the relatively low redox kinetics for the C═O groups at the middle voltage plateau.

FIGURE 4.

Li⁺ storage and transport mechanism in heterocyclic TTQ cathodes. (a) ESP‐mapped molecular van der Waals surface. (b) Capacitive contribution (shaded regions) from CV at a scan rate of 0.1 mV s⁻¹. (c) Capacitive contribution percentages versus scan rates of 0.1−0.5 mV s⁻¹. (d) Nyquist plots from EIS and equivalent circuit fits (solid line). (Inset) Linear fit (R ² > 0.99) of the real part of impedance (Z') versus the root of low frequency (ω^−0.5) for Li⁺ diffusion coefficient calculation. (e) Arrhenius plot for Li⁺‐desolvation activation energies in organic cathodes. (f) Arrhenius plot for Li⁺‐diffusion activation energies in organic cathodes.

The extraordinary rate performance prompted us to investigate electrochemical reaction kinetics. By means of CV measurements at various scan rates (Figure S32a–c), we extracted the kinetic parameter b from the slope in log‐plots of the current response to redox peaks against the applied scan rates (Note S1). As established, the b value equal to 1.0 indicates surface‐controlled pseudocapacitive behavior, while 0.5 signifies diffusion‐limited Randles–Ševčík kinetics [64]. All heterocyclic TTQ electrodes gave the b values approaching 1.0 (Figure S32d–f), indicating that their redox chemistry is dominated by fast pseudocapacitive processes. Quantitative analysis of capacitive contributions corroborated this finding. Distinct from OTTQ, STTQ cathodes donated capacitive contributions over 90% at a scan rate of 0.1 mV s⁻¹ (Figure 4b), which further increased to above 96% by applying 0.5 mV s⁻¹ (Figure 4c).

We derived Li⁺‐diffusion coefficients (D _Li ⁺) of electrode materials from the low‐frequency linear region in Nyquist plots obtained via EIS (Figure 4d and Note S2) [65]. Beyond delivering larger capacitive contributions, STTQ‐2 showed a higher D _Li ⁺ of 6.29 × 10⁻⁹ cm² s⁻¹ and compared to STTQ‐1 (2.40 × 10⁻⁹ cm² s⁻¹; Table S5). Notably, the charge transfer within the STTQ cathodes boosted upon cycling (Figure S33). By contrast, the substantially lower D _Li ⁺ (2.03 × 10⁻¹⁰ cm² s⁻¹) and larger R _ct (Figure 4d and Table S5) of OTTQ rationalize its inferior rate capability. These results collectively establish that enhanced Li⁺ transport and rapid charge transfer are the key factors governing the superior rate performance of the STTQ cathodes. Further employing R _ct and D _Li ⁺ values derived from temperature‐dependent EIS (Figures S34 and S35) into Arrhenius equation (Note S3), we calculated activation energies for Li⁺ desolvation (E _{a, ct}) and diffusion (E _{a, D} ), respectively. As shown in Figure 4e,f, both Li⁺ desolvation and diffusion barriers in STTQs were significantly lower than those of OTTQ across all test temperatures. Combined with the difference in the redox energy landscape (Figure S30), these findings clearly elucidate the critical role of lithiophilic dithioether heterocycles in rapid and stable Li⁺ storage.

2.5. Practical Implementation

Encouraged by the impressive outcome of STTQ‐1, we sought to fabricate organic electrodes with high mass loading to assess its practicability. When increasing the areal mass loading from 1.1 to 18.6 mg cm⁻², the organic cathode containing 60 wt% of STTQ‐1 delivered specific capacities decreasing from 268 to 192 mAh g⁻¹ at 0.3C (Figure 5a). At a mass loading of 2.0 mg cm⁻², the organic cathode still achieved 79% SoC in 81 s at 30C (Figures 5b and S36), showing high‐rate performance comparable to that under low loading conditions (Figure 3b). However, further increasing the content of STTQ‐1 to 70 wt% within the cathode compromises the rate performance, resulting in a limited SoC of 77% at 10C (Figure S37). Nevertheless, organic cathodes with mass loading exceeding 2.0 mg cm⁻² operated stably for 100 cycles without distinct capacity fading across a wide temperature range from −50°C to 60°C (Figures 5c and S38). Even at an ultrahigh mass loading of 18.6 mg cm⁻², the organic cathode still operated reliably at 60°C (Figure S39). Finally, we assembled a full battery using lithiated graphite as the anode, which achieved a specific capacity of 248 mAh g⁻¹ at 1C and sustained stable operation over 100 cycles (Figure S40). These results demonstrate the promising potential of STTQ‐1 for practical applications and strong tolerance to extreme environments.

FIGURE 5.

Practical implementation of the STTQ‐1 cathode in Li–organic batteries. (a) Galvanostatic charge/discharge profiles at a current density of 60 mA g⁻¹ with cathode mass loadings of 1.1−8.1 mg cm⁻². (b) Charge (circles) and discharge (dots) capacities at charge rates of 0.3C−30C with a mass loading of 2.0 mg cm⁻². (c) Cycling performance (dots) and coulombic efficiency (circles) at mass loadings of 2.5−6.6 mg cm⁻² were tested at 60°C (red), 25°C (grey) and −50°C (blue). The current density was set to 0.3 A g⁻¹ at 60°C and −50°C, and 0.15 A g⁻¹ at 25°C. (d) Schematic of a laminated Li–organic pouch cell with multilayered organic cathodes and Li‐metal anodes. (e) Galvanostatic charge/discharge profiles of an 0.1‐Ah‐level Li–organic pouch cell in a potential window of 1.5−3.5 V vs. Li/Li⁺ at a current density of 1.5 mA cm⁻² (0.3C). (f) Charge capacities of a pouch cell at 0.3, 1, 2, 4, and 6C (1C = 5 mA cm⁻²). (g) Photographs of an iPhone and an LED lamp powered by Li–organic pouch cell under bending, puncturing and cutting conditions.

To pursue the fast‐charging goal, we further assembled a 0.1‐Ah‐level Li–organic pouch‐type cell (4 cm × 5 cm) consisting of multilayered organic cathodes and Li‐metal anodes (Figure 5d). At a low current density (1.5 mA cm⁻²), the laminated pouch cell achieved a reversible areal capacity of ∼5.0 mAh cm⁻² (Figure 5e), surpassing the performance metrics of commercial LIBs (4 mAh cm⁻²). Remarkably, the cell, when charged at 2C (10 mA cm⁻²) for 24 min and at 6C (30 mA cm⁻²) for 6.5 min, stored areal capacities of ∼4.0 mAh cm⁻² and ∼3.3 mAh cm⁻², corresponding to 80% and 66% SoC, respectively (Figures 5f and S41). Meanwhile, the cell sustained superior cycling stability with ∼100% capacity retention for 100 cycles (Figure S42). In practical scenarios, our Li–organic battery sustainably powered an iPhone and an LED lamp under bending, puncturing and even cutting conditions (Figure 5g), underscoring its excellent operational stability and safety. These metrics provide strong support on developing practical fast‐charging Li–organic batteries [66].

3. Conclusion

In summary, we have tailored three heterocycle‐extended triptycene tribenzoquinone derivatives as high‐performance organic cathode materials. These molecular blocks self‐assemble into lamellar, porous, yet short‐range ordered 2D supramolecular polymers. Concurrently, the lithiophilic sulfur‐heterocycle significantly boosts Li⁺ desolvation and diffusion. Coupled with a cross‐flow Li⁺ transport mechanism and dominant pseudocapacitive behavior, this supramolecular engineering improves comprehensive electrochemical performance, particularly in fast charging and long‐term cycling across a wide temperature range. Furthermore, a Li–organic pouch cell is fabricated to demonstrate minute‐level fast charging and stable cycling under high‐mass‐loading conditions. This work provides a blueprint for the structural design of electrode materials used in next‐generation sustainable energy storage devices.

Author Contributions

L.L., X.D., and Z.C. conceived the idea and designed the experiments. L.L. conducted the synthesis, characterization, and measurements. Q.C. performed the theoretical calculation. X.D. and Y.M. conducted partial synthesis. X.Z., H.H., L.Q., and L.P. participated in the data analysis and discussion. L.P. and Z.C. led the project. L.L., X.D., and Z.C. drafted and revised the manuscript.

Conflicts of Interest

Tsinghua University and Z.C., L.L. and X.D. have filed a patent (no. ZL202411478634.8) for the synthetic method of organic cathodes reported in this paper. The other authors declare no conflict of interest.

Supporting information

Supporting File 1: anie73625‐sup‐0001‐SuppMat.pdf.

Supporting File 2: anie73625‐sup‐0002‐Data.zip.

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.