An Insensitive Energetic Material as a High‐Performance Organic Cathode Toward Dual‐Mode Batteries

ABSTRACT

Bridging long‐duration electrochemical power delivery with on‐demand, ultrafast explosive output within a single material could enable next‐generation mission‐critical power systems. Here, we report an insensitive yet energetic small molecule, 4,4′,6,6′‐tetramino(azo)‐1,3,5‐triazine (TAAT) as a high‐performance organic cathode for batteries with dual‐mode energy release. Guided by a modular “function‐by‐design” strategy, TAAT concurrently exhibits low solubility, reversible Li⁺ storage, triggerable explosive output, and high insensitivity. In lithium batteries, TAAT delivers 215 mAh g⁻¹ with a ≈ 3.0 V discharge plateau and sustains stable cycling over 700 cycles; TAAT||Li pouch cells power a mini quadcopter. Beyond electrochemistry, TAAT exhibits a detonation velocity of 7505 m s⁻¹ and detonation pressure of 18.4 GPa, while remaining thermally and mechanically insensitive (T_d ≈ 327 °C; impact >40 J; friction >360 N). The energetic response can be initiated by hot wire, laser, or detonator stimuli. These results establish TAAT as a proof‐of‐concept dual‐mode energy‐release material, advancing mission‐tailored battery technologies.

TAAT, an insensitive nitrogen‐rich energetic molecule, enables dual‐mode energy release in lithium batteries. As an organic cathode, it delivers a ≈3.0 V plateau, 215 mAh g−¹ capacity, and >700‐cycle durability. Beyond electrochemical power supply, TAAT offers triggerable explosive output (7505 m s−¹, 18.4 GPa) while maintaining excellent thermal and mechanical insensitivity, integrating mission‐stage power and terminal energetic response.

1. Introduction

Humankind has long sought to control both the mode and rate of energy release to meet diverse application needs. The rate of energy release is quantified by power density (W kg⁻¹), which represents the amount of energy delivered per unit mass per unit time. Conventional batteries rely on electrochemical reactions to provide stable energy output with relatively low power densities (10²–10³ W kg⁻¹), making them ideal for sustained power supply [1, 2]. In contrast, energetic materials can convert stored chemical energy into explosive output within microseconds, reaching instantaneous power densities up to 10⁹ W kg⁻¹, 5–7 orders of magnitude higher than those of conventional batteries, making them essential for rapid, destructive energy delivery [3]. Bridging these fundamentally different energy‐release behaviors into one material platform could unlock new “mission‐tailored” power technologies.

Many mission‐critical systems—loitering munitions and self‐destructing microelectronics—must operate reliably for extended periods (e.g., cruise, sensing, communication) yet initiate rapid energy release at the terminal stage. Today, this is usually achieved by integrating separate battery and energetic modules, which increases system weight and volume, complicates packaging and control [4]. We thus envision a battery concept that provides stable electrochemical power under normal operation but can be switched, on demand, into an energetic response mode at the terminal stage (Figure 1A) [5]. Realizing this concept hinges on developing dual‐mode energy‐release materials—defined here as energetic energy storage materials (EESMs)—that combine reversible electrochemical energy storage with triggerable explosive output in a single material architecture. In this context, “dual‐mode” denotes two temporally separated and externally selectable functions: sustained electrochemical power delivery during normal operation and energetic release only upon deliberate external triggering at the terminal stage. Ideal EESMs must strike a balance among electrochemical energy‐storage performance, destructive capability, and handling safety (Figure 1B). Electrochemical energy‐storage performance is determined by the average discharge voltage (V), specific capacity (C), and cycle life (N) [1]. Destructive capability is characterized by detonation velocity (V_d) and detonation pressure (P), which quantify the intensity of ultrafast energy release [6]. Handling safety, in turn, requires a high thermal decomposition temperature (T_d) and low mechanical sensitivity, as reflected by high impact sensitivity (IS) and friction sensitivity (FS) thresholds, to minimize the risk of accidental initiation [7, 8]. However, achieving harmony among these often‐conflicting demands is inherently challenging, given the fundamental differences in material structures and energy release mechanisms between electrochemical energy storage and energetic materials.

FIGURE 1.

Dual functionality and the design criteria of EESMs. (A) Schematic of different energy‐release modes across power‐output regimes, alongside the dual‐function concept of EESMs and its potential applications. (B) Performance‐design framework for EESMs.

To meet the requirements of EESMs, small‐molecule organic redox‐active materials offer intrinsic advantages because their structures are programmable with well‐defined structure−property relationships [9, 10, 11, 12]. In a single molecular scaffold, redox‐active motifs (e.g., carbonyl, imine, and azo groups) can be integrated with energetic motifs (e.g., nitro groups and N‐rich heterocycles), allowing a modular “function‐by‐design” strategy in which each individual building block is assigned to a dedicated role—electrochemical reversibility, triggerable explosive output, or handling safety. In addition, intermolecular interactions (e.g., hydrogen bonding and π–π stacking) can promote self‐assembly into ordered, densely packed supramolecular networks, which helps regulate solubility, packing density, and thermal/mechanical robustness. Collectively, these features make small molecules a compelling and versatile platform for co‐optimizing redox behavior and energetic performance within one material [7, 13, 14].

In this study, we present 4,4′,6,6′‐tetramino(azo)‐1,3,5‐triazine (TAAT), a nitrogen‐rich small molecule, as a proof‐of‐ concept EESM for lithium‐battery cathode. Structurally, TAAT consists of two amino‐substituted triazine rings bridged by an azo linkage (─N═N─), which serves both as a redox‐active center and an energetic structural motif. As an energy storage material, the TAAT cathode delivers a ≈ 3 V (vs. Li⁺/Li) discharge plateau and a reversible capacity of 215 mAh g⁻¹, maintaining 72% of its initial capacity after 700 cycles at 0.5 C rate. A TAAT‐based pouch cell further powers sustained hovering of a mini quadcopter, verifying its practical feasibility. As an energetic material, TAAT exhibits a detonation velocity of 7505 m s⁻¹ and a detonation pressure of 18.4 GPa, comparable to benchmark TNT (7236 m s⁻¹ and 20.6 GPa) [15]. TAAT also responds vigorously under hot‐ignition, laser‐initiation, and detonator tests, confirming its energetic functionality. Meanwhile, it shows excellent thermal stability (T _d ≈ 327°C) and mechanical insensitivity (IS >40 J, FS >360 N). Collectively, these results establish TAAT as a promising EESM that bridges the paradigms of electrochemical energy storage and energetic materials, laying a material foundation for next‐generation mission‐critical power sources.

2. Results and Discussion

2.1. Configuration of Dual‐Mode Energy‐Release Battery Based on EESM Cathode

In dual‐mode energy‐release batteries, the EESM‐based cathode is engineered to be the primary contributor of the energetic response, whereas the anode and electrolyte mainly act as secondary reactants that can further enhance heat release upon triggering (Figure 2A). We therefore begin with the cathode design. Conventional Li‐ion cathodes—including transition‐metal oxides [16], sulfur‐based materials [17], and redox‐active organics [10]—excel at reversible Li‐storage but lack intrinsic energetic functionality, limiting their ability to deliver shock‐generating output on demand (Figure 2B, left). By contrast, traditional energetic compounds (e.g., polynitro compounds and nitrogen‐rich compounds) store high chemical energy that can be released on ultrafast timescales (Figure 2B, right). Polynitro systems rely on intense inter/intramolecular redox reactions, in which nitro groups act as internal oxidizers [18, 19, 20, 21], while nitrogen‐rich systems leverage cleavage of high‐energy bonds (e.g., azo and azide) or strained N ‐heterocyclics to rapidly liberate N₂ and produce high detonation velocities and pressures [22, 23, 24, 25, 26]. These features motivate incorporating energetic motifs into redox‐active cathode scaffold to couple reversible electrochemistry with a triggerable energetic mode, which is a central challenge for dual‐mode batteries.

FIGURE 2.

Evaluation of conventional energetic materials as cathodes in Li–metal batteries. (A) Schematic of the dual‐mode energy‐release battery and operating principle. (B) Classification of conventional Li‐ion battery cathodes (left) and energetic materials (right), positioning EESMs in the middle region. (C) Mass distribution of a representative lithium‐based battery. (D) ¹H NMR spectra and (E) optical microscope images of conventional energetic materials. (F) Visual inspection of solubility and (G) UV–vis spectra of conventional energetic materials in 1 M LiTFSI in DOL/DME electrolyte. (H) GCD profiles of conventional energetic materials used as cathode materials at 0.05 C and (I) their corresponding cycling performance in 1 M LiTFSI in DOL/DME electrolyte.

Lithium metal is selected as anode for its ultralow redox potential (−3.04 V vs. SHE) and high specific capacity (3860 mAh g⁻¹) [27]. Under triggered conditions, its high reactivity enables rapid secondary exothermic reactions that can augment the cathode‐initiated energetic event [28]. We employ LiClO₄/EC−DEC as the electrolyte since it offers good ionic conductivity and interfacial compatibility during normal operation [29]; under heating, LiClO₄ can decompose to liberate oxidizing species that, together with flammable EC/DEC solvents, accelerate exothermic reactions and further enhances destructive energy release (Figure S1) [30].

It is important to distinguish detonation from combustion. Detonation is a supersonic, shock‐front‐driven process, characterized by detonation velocity and pressure. It delivers ultrahigh power densities >10⁹ W kg⁻¹. In contrast, combustion proceeds far more slowly (10⁵–10⁷ W kg⁻¹) and does not produce shock waves (Figure 1A) [31]. During conventional thermal runaway of lithium batteries, cell components (e.g., Li anode, electrolyte, and cathode) primarily act as fuels and undergo combustion rather than detonation, resulting in limited shock‐generating capability. In a dual‐mode energy‐release battery architecture, however, the EESM‐based cathode is designed to provide a detonative event, while combustion of the anode/electrolyte contributes secondary energy augmentation, yielding a stronger In practical lithium−metal batteries, the cathode typically constitutes the largest mass fraction, exceeding the electrolyte, lithium anode, and other components (Figure 2C) [32]. Consequently, equipping the cathode with energetic functionality is the most effective route to maximize total destructive output, and thus forms the focus of this work.

2.2. Benchmarking Conventional Energetic Materials as Cathodes in Li–Metal Batteries

We next investigated several representative energetic materials, including 2,4,6‐trinitrotoluene (TNT), hexogen (RDX), octogen (HMX), hexanitrohexaazaisowurtzitane (CL‐20), as potential cathodes in lithium batteries. The chemical structures and purity of these compounds were confirmed by ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy (Figures 2D and S2–S9). Optical microscopy revealed crystalline morphologies ranging from tens to hundreds of micrometers (Figure 2E). Solubility tests coupled with UV–vis analysis showed substantial dissolution in common ether‐based lithium electrolytes, with solubilities exceeding 7 mg mL⁻¹ for HMX and 15 mg mL⁻¹ for TNT—far exceeding the threshold compatible with stable battery operation (Figure 2F,G). Galvanostatic charge/discharge (GCD) tests were further performed on these cathodes. HMX and CL‐20 exhibited distinct discharge plateaus at 2.4 V and 2.7 V (vs. Li⁺/Li), respectively, whereas TNT and RDX exhibited sloping voltage profiles (Figure 2H) [33, 34, 35]. The corresponding discharge capacities were 455 mAh g⁻¹ (TNT), 85 mAh g⁻¹ (RDX), 318 mAh g⁻¹ (HMX), and 220 mAh g⁻¹ (CL‐20). Despite their relatively high initial discharge capacities, the capacities dropped sharply in subsequent cycles, and all four materials lost cyclability within only a few cycles (Figures 2I and S10). This rapid loss of rechargeability likely arises from a combination of (i) structural/chemical instability of reduced nitro species—especially for polynitro frameworks with complex, multi‐step reduction pathways, and (ii) severe dissolution‐induced shuttle effects, which together accelerate capacity fading and render the reactions largely irreversible. Therefore, traditional energetic materials are unsuitable for use as cathodes in rechargeable lithium batteries.

2.3. Molecular Design and Material Characterization of TAAT

We adopted a modular “function‐by‐design” strategy to develop TAAT, a nitrogen‐rich molecule with a rigid, π‐conjugated, and highly symmetric framework (Figure 3A). TAAT integrates three cooperative modular units—an azo linkage, two electron‐deficient triazine rings, and four peripheral amino groups—enabling the concurrent tuning of redox behavior, structural stability, and energetic response within a single molecular scaffold. The azo linkage provides a well‐defined, reversible 2e⁻ redox center, ensuring efficient Li⁺ storage. Meanwhile, the N‐rich motif contributes to the energetic character of TAAT by releasing N₂ rapidly under initiation conditions [36]. The triazine rings act as strong electron‐withdrawing cores that effectively lower the LUMO level and thereby raise the redox potential, affording a relatively high discharge voltage (Figure S11); their rigid, nitrogen‐rich backbones also increase the overall nitrogen content and enhance structural robustness. Finally, the amino groups act as hydrogen‐bond donors, forming an extended hydrogen‐bonding (N─H⋯N) network with triazine units, which suppresses material dissolution and improves structural stability. Through this rational integration, TAAT achieves a compact and atom‐efficient architecture with a clear structure–function relationship, making it a promising high‐performance EESM.

FIGURE 3.

Molecular design and spectroscopic characterization of TAAT. (A) Molecular design of TAAT as an EESM. (B) ¹H, ¹³C, and ¹⁵N NMR spectra of TAAT. (C) FTIR spectra of TAAT. (D) UV–vis spectra of TAAT in blank electrolyte, with inset showing the Beer–Lambert plots overall output.

The successful synthesis of TAAT was confirmed by ¹H, ¹³C, and ¹⁵N NMR spectra (Figures 3B and S12–S14). In the ¹H spectrum, the distinct peak at 7.18 ppm is assigned to the protons of the amino (─NH₂) group. FTIR analysis further confirms the presence of characteristic ─NH₂ stretching vibrations at 3460 cm⁻¹ and 3314 cm⁻¹, as well as the aromatic N═N stretching band at 1520 cm⁻¹, in agreement with the XPS results (Figures 3C and S15). XRD patterns indicate the high crystallinity of TAAT, while SEM and TEM images reveal flake‐like morphologies with lateral dimensions of several hundred nanometers (Figures S16 and S17). TAAT shows negligible dissolution in commonly used EC/DEC mixed solvents by visual inspection, and quantitative UV–vis measurements show an extremely low solubility of 45 µg mL⁻¹ (Figures 3D and S18). Dissolution of organic electrode materials in non‐aqueous electrolytes has long impeded their practical deployment in rechargeable batteries. Previous remedies, including polymerization [37], polarity tuning [38], electrolyte modification [39], and physical confinement [40], can alleviate this issue but typically involve complicated syntheses, high costs, or the introduction of considerable inactive mass. In contrast, our molecular design intrinsically suppresses dissolution via engineered weak intermolecular interactions, offering a simple yet effective solution without sacrificing electrochemical performance [41, 42].

2.4. Electrochemical Performance of TAAT||Li Batteries and Redox Mechanism of TAAT

We further evaluated the electrochemical performance of TAAT in lithium–metal batteries. The GCD profiles exhibit a stable discharge plateau at ∼ 3 V (vs. Li⁺/Li) and a reversible capacity of 215 mAh g⁻¹, approaching its theoretical value of 216 mAh g⁻¹ (Figures 4A and S19). Molecular electrostatic potential (ESP) analysis clarified the electron density distribution within TAAT, revealing that the strongly electron‐withdrawing triazine rings deplete electron density around the azo bond. This polarization effect facilitates azo bond reduction, contributing to a high discharge voltage. Figure 4B and Table S1 compare the operating voltages and capacities of representative organic and inorganic cathodes for lithium‐ion batteries. Although TAAT displays a slightly lower energy density than the conventional inorganic cathodes, such as LiCoO₂ and LiNi_0.6Co_0.2Mn_0.2O₂ (NMC622), it surpasses these conventional inorganic materials in specific capacity. Benefiting from its composition of lightweight elements (C, H, and N), TAAT offers superior gravimetric performance and distinct advantages for lightweight energy‐storage applications [10]. Furthermore, TAAT is synthesized from earth‐abundant, cost‐effective, and environmentally benign raw materials, underscoring its sustainability advantages compared with the resource‐intensive and toxic metal chemistry of inorganic cathodes [43]. In contrast to most organic cathodes, which typically face a trade‐off between voltage and capacity, TAAT simultaneously achieves a notable material‐level energy density of 645 Wh kg⁻¹.

FIGURE 4.

Electrochemical performance and redox mechanism of TAAT in lithium batteries. (A) GCD profile of TAAT, inset shows the calculated ESP distribution. (B) Ashby plot comparing the electrochemical performance of TAAT with other cathode materials reported for lithium‐ion batteries. (C) CV profiles of TAAT under different scan rates. (D) Rate performance. (E) Cycling performance at 0.5 °C. (F) Self‐discharge behavior. (G) Low‐temperature performance. (H) Photograph and schematic of the operando Raman cell used to monitor the TAAT electrode during cycling. (I) Operando Raman spectra recorded during discharge/charge. (J) Ex situ FTIR spectra, (K) ex situ XPS spectra (Li 1s and N 1s), and (L) ex situ ⁷Li NMR spectra at selected states.

The kinetics of TAAT was evaluated through CV tests. As the scan rate increased from 0.1 to 2.0 mV s⁻¹, TAAT displayed high electrochemical reversibility (Figure 4C). Analysis of the relationship between peak current (i_p ) and scan rates (υ), described as i_p = aυ^b , where a and b are constants, yielded calculated b‐values of 0.93 and 0.97, suggesting a capacitive‐controlled lithium storage mechanism favorable for fast charge transfer (Figure S20). Figures 4D and S21 present the rate performance of the TAAT||Li battery, which achieves a high capacity of 170 mAh g⁻¹ even at 20 °C. Long‐term cycling tests further confirmed the durability of TAAT, maintaining 72% of initial capacity after 700 cycles at 0.5 °C (Figure 4E and S22 and S23). To assess the storage stability of TAAT‐based batteries, self‐discharge tests were conducted (Figures 4F and S24). After being stored at open‐circuit voltage (OCV) for 24 h, the fully charged TAAT||Li battery can still deliver 94.4% of its initial capacity upon discharge to 1.8 V. This minimal capacity loss reflects the negligible dissolution and shuttle effect, highlighting the material's potential for long‐term stability in practical scenarios that demand extended shelf‐life and immediate readiness. Low‐temperature performance is critical for applications in harsh environments such as high‐altitude or winter missions. At −10°C, TAAT retained 78% of its room‐temperature capacity, confirming reliability under sub‐zero conditions (Figures 4G and S25). To further improve low‐temperature performance, further work should focus on replacing EC with solvents possessing lower melting points [44].

To monitor the structural evolution of TAAT during cycling, operando Raman spectra was employed due to its high sensitivity to azo bonds. Figure 4H illustrates the customized operando Raman cell setup. Figure 4I presents the time‐resolved evolution Raman spectra for the TAAT electrode. The pristine state exhibits a prominent peak at 1520 cm⁻¹, corresponding to the stretching vibration of ─N═N─ bond. This peak gradually attenuates upon discharging and re‐emerges during charging, indicating the reversible transformation between ─N═N─ and ─LiN─NLi─. This reversible structural change was further validated by ex situ FTIR spectroscopy at selected discharge and charge states (Figure 4J). Ex situ Li 1s XPS analysis reveals a distinct Li peak at 56.0 eV upon discharge, indicative of Li⁺ coordination with reduced TAAT species (Figure 4K, left). The N 1s spectra reveal peaks at 401.0 and 399.0 eV in the pristine state, standing for ─N═N─ and C─N/N─H groups, respectively (Figure 4K, right) [45]. A new peak emerges at 399.8 eV after discharge, assigned to the formation of ─LiN─NLi─. This peak diminishes upon charging, indicating the reversible de‐coordination of Li⁺ ions from the TAAT structure. Consistently, ⁷Li NMR spectra show a similar trend to the Li 1s XPS result, also confirming the reversible Li coordination and de‐coordination process (Figure 4L). Additionally, XRD analysis reveals that TAAT undergoes a crystalline‐to‐amorphous transition upon cycling (Figure S26).

2.5. Thermal Behavior, Safety Metrics, and Structure–Property Relationships of TAAT

Subsequently, we systematically evaluated the thermal decomposition behavior of TAAT. Thermogravimetric−differential scanning calorimetry coupled with mass spectrometry (TG−DSC−MS) and Fourier transform infrared spectroscopy (TG−DSC−FTIR) were employed to monitor real‐time mass loss and gaseous decomposition products during heating [22]. To avoid interference from nitrogen gas as a carrier gas, experiments were conducted under an oxygen atmosphere. Figure 5A depicts a sharp weight loss of 47.3% at 327°C in the TG curve, accompanied by a pronounced exothermic peak in the DSC curve, indicating rapid thermal decomposition and gas generation. Concurrently, the MS spectrum shows a strong signal at m/z = 28, corresponding to nitrogen gas produced from the cleavage of azo bonds and triazine rings in the TAAT framework. Nitrogen gas is a common decomposition product in nitrogen‐rich energetic compounds [46]. As the temperature further increases, weak yet persistent signals at m/z = 30 and m/z = 44 appear above 400°C, assigned to NO and CO₂, respectively, suggesting partial oxidation of residual carbonaceous species. TG−DSC−FTIR spectra show a distinct absorption peak at ∼ 2337 cm⁻¹, confirming CO₂ evolution consistent with the MS results (Figures 5B and S27 and S28).

FIGURE 5.

Thermal behavior, safety performance, and structural analysis of TAAT. (A) TG−DSC−MS profiles of TAAT in O₂ at a heating rate of 10°C min⁻¹. (B) FTIR contour map of gaseous products evolved during TAAT decomposition in O₂ heated at 10°C min⁻¹. (C) Temperature–time (T–t) and pressure–time (P–t) profiles of TAAT from ARC test under adiabatic conditions. (D) Corresponding dT/dt–T and dP/dt–T profiles from ARC test. (E) Friction sensitivity test. (F) Impact sensitivity test. (G) Hydrogen‐bond network (top) and π–π stacking (bottom) in the TAAT crystal. (H) π‐LOL isosurface map (top) and color‐filled map at 0.5 Å above the ring plane of TAAT (bottom). (I) Radar chart comparing the energetic performance of TAAT and TNT.

To gain further insight into the decomposition behavior of TAAT under adiabatic heat‐accumulation conditions, an accelerating rate calorimetry (ARC) test was performed (Figure S29) [47]. As an adiabatic abuse‐safety test, ARC probes the response of TAAT under a worst‐case thermal‐abuse scenario and therefore complements, rather than contradicts, its handling safety during routine storage and battery operation. Figure 5C shows the temperature–time (T–t) curve, divided into three stages: (i) a heat–wait–search (HWS) stage to detect the onset of self‐heating, (ii) a self‐heating stage initiated at 500 min (170°C) with gradual exothermic decomposition, and (iii) a thermal runaway stage marked by a rapid, uncontrollable temperature surge peaking at 305°C. Concurrently, the pressure–time (P–t) curve shows a significant pressure buildup, reaching a maximum at 49 bar. Derivative curves, including dT/dt–T and dP/dt–T curves, indicate the maximum self‐heating rate (2074°C min⁻¹) and gas generation rate (2746 bar min⁻¹) are both reached at 305°C (Figure 5D). Constrained electrical explosion test also detected a pressure buildup from the P–t curve (Figure S30). Mechanical sensitivity tests were carried out to further evaluate the safety of TAAT under practical conditions (Figure 5E,F). The impact and friction sensitivities were measured to be >40 J and >360 N, respectively; no explosion was observed, and only slight decomposition, evidenced by discoloration, occurred. Such low sensitivity ensures good safety compatibility of TAAT‐based cathode during normal operation in power supply applications.

The exceptional safety performance of TAAT under thermal, impact, and friction stimuli is attributed to its robust intermolecular hydrogen‐bonding (HB) network, π–π stacking, and pronounced aromaticity. As illustrated in Figure 5G, the HB network involves N─H⋯N_triazine (1.85 Å) and N─H⋯N_amino (2.85 Å) interactions, further reinforced by strong π–π stacking with an interlayer distance of 3.2 Å. π‐electron localized orbital locator (π‐LOL) analysis confirms extensive and uniform π‐electron delocalization across the azo‐bridged triazine framework, indicative of highly aromatic character (Figure 5H). Figure 5I benchmarks TAAT against the established secondary explosive TNT in terms of heat of formation (ΔH_f), decomposition temperature (T_d), detonation velocity (V_d), detonation pressure (P), and density (ρ). Compared with TNT, TAAT shows higher ΔH_f and V_d, while delivering a comparable V_d of 7505 m s⁻¹ and P of 18.4 GPa, highlighting its promising energetic potential (Table S2).

2.6. Practical Demonstrations of TAAT

To evaluate the practical applicability of TAAT in real‐world conditions, we fabricated a TAAT||Li pouch cell and tested its ability to power a mini quadcopter drone. As shown in Figure 6A,B, the pouch cell adopts a multilayer stacked design, comprising double‐side‐coated TAAT cathodes and 100 µm‐thick Li metal anodes, both with dimensions of 1.5 cm × 3.5 cm. The cell exhibited an OCV of 3.22 V (Figure 6C). The quadcopter used for demonstration weighs 74.6 g and measures 26 cm × 26 cm (Figure 6D). Upon connecting the TAAT||Li, the quadcopter's indicator lights illuminated immediately, but lift‐off failed since the four motors require a high transient current at startup that exceeds the cell's instantaneous discharge capability (Figure S31). To quantify the current threshold, a benchtop power supply was used to measure the minimum currents needed for takeoff and sustained hovering, respectively (Figure S32). Under 3 V, the take‐off current reached 2.2 A, while only 1.5 A was needed to sustain stable flight, indicating a markedly lower current demand after liftoff. With initial assistance from a benchtop power supply during take‐off, the quadcopter was subsequently powered solely by the TAAT||Li cell, achieving sustained hovering and demonstrating its capability for continuous energy delivery (Figure 6E).

FIGURE 6.

Practical demonstrations of TAAT: pouch cell as power supply and energetic initiation tests. (A) Schematic of the multilayer TAAT||Li pouch cell. (B) Photographs of the assembled pouch cell, TAAT cathode, and Li anode. (C) OCV measurement of the TAAT||Li pouch cell. (D) Mass and dimensions of the quadcopter drone used for the power‐supply demonstration. (E) In‐flight photograph of the quadcopter powered by the TAAT||Li pouch cell. (F) Schematic of the hot‐ignition setup. (G) Time‐resolved frames from the hot‐ignition test. (H) Schematic of the laser‐ignition test. (I) Sequential frames showing flame growth during laser ignition test. (J) Schematic of the detonator‐initiation test. (K) Front and top views of the detonator initiation test setup. (L) Photograph captured during detonator initiation. (M) Lead plates before and after explosion.

The energetic performance of TAAT was further evaluated via a series of explosive tests. In the hot‐ignition test, a nichrome resistive wire was used to transfer heat energy to the TAAT powder, triggering intense burning captured by high‐speed imaging, characteristic of a deflagration‐type reaction (Figures 6F,G and Movie S1). To explore the initiation behavior under more controlled yet intense stimuli, a laser initiation test was carried out [48]. A pelletized TAAT sample was clamped between two steel nuts and irradiated with 60 W laser (Figures 6H and S33 and Movie S2). The localized energy delivered by laser triggered a violent, self‐sustained combustion, with an initiation delay of 10 ms, demonstrating a high sensitivity to laser stimulation (Figure 6I). More stringently, a detonator initiation test was conducted under confined conditions similar to real‐world scenarios (Figure 6J) [49]. As shown in Figure 6K, the explosive charge column exploded violently upon electric detonator triggering, producing a bright flash, sharp explosive sound, and high‐pressure gas release (Figure 6L and Movie S3). The blast perforated a 2 mm‐thick, 3.5 cm‐diameter lead plate with a 1.8 cm‐diameter hole, confirming TAAT's strong detonation performance and potential as a practical secondary explosive (Figure 6M).

While this study demonstrates the material‐level energetic performance of TAAT, translating these properties to practical electrodes and full cells remains challenging. Critical issues include (i) developing reliable and controllable triggering of the energetic mode in EESM‐based batteries, which may require external initiation designs; and (ii) maximizing device‐level explosive output—namely, systematically endowing other cell components (conductive additives, binders, separators, current collectors, and packaging) with energetic properties. These engineering aspects extend beyond the scope of the present study yet are critical for advancing dual‐mode energy‐release battery technologies. Nonetheless, our results provide a first proof‐of‐concept that TAAT can serve as a viable EESM, laying a foundation for further electrode and device integration.

3. Conclusion

In summary, we present 4,4′,6,6′‐tetramino(azo)‐1,3,5‐triazine (TAAT), an azo‐bridged, nitrogen‐rich molecule, as a proof‐of‐concept energetic energy storage material (EESM) used in lithium batteries. Guided by a modular “function‐by‐design” strategy, TAAT was developed by integrating azo redox center with electron‐deficient triazine and hydrogen‐bonding amino motifs, enabling the concurrent tuning of electrochemical performance, energetic response, and handling safety within one scaffold. The TAAT cathode delivers ≈ 3.0 V discharge voltage, 215 mAh g⁻¹ capacity, and >700‐cycle durability. A TAAT‐based pouch cell powers a micro‐quadcopter, demonstrating its practical power supply capability. Beyond electrochemical performance, TAAT achieves a detonation velocity of 7505 m s⁻¹ and a detonation pressure of 18.4 GPa, while maintaining high thermal and mechanical insensitivity (T _d = 327°C; FS >360 N; IS >40 J). Upon hot‐wire, laser, or detonator initiation, TAAT delivers a powerful explosive output. By uniting stable electrochemical operation with an on‐demand energetic response, TAAT establishes a new design paradigm for dual‐mode chemical energy release, opening opportunities for next‐generation mission‐tailored battery systems.

Author Contributions

Jiapeng Zhao: investigation, methodology, formal analysis, software, data curation, validation, writing – review and editing. Wenjin Zhang: methodology, formal analysis, data curation, software, writing – review and editing. Yuxin Xue: methodology, writing – review and editing. Zhihao Liu: methodology, writing – review and editing. Weixiao Ji: writing – review and editing, writing – original draft, conceptualization, project administration, funding acquisition, supervision, resources, visualization, data curation, validation, investigation, formal analysis. Chenghui Sun: writing – review and editing, formal analysis. He Huang: conceptualization, writing – review and editing, funding acquisition, visualization, project administration, resources, supervision, investigation, validation, formal analysis, data curation. Siping Pang: conceptualization, writing – review and editing, supervision.

Conflicts of Interest

The authors declare no conflicts of interest.

Supporting information

Supporting File 1: anie72801‐sup‐0001‐SuppMat.docx.

Supporting File 2: anie72801‐sup‐0002‐vedioS1.mp4

Supporting File 3: anie72801‐sup‐0003‐vedioS2.mp4.

Supporting File 4: anie72801‐sup‐0004‐vedioS3.mp4.

Data Availability Statement

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