A team led by Yukai Chang at Henan Polytechnic University has recently conducted systematic research on the innovative design of freeze‑tolerant micro‑supercapacitors (MSCs) and integrated flexible sensing systems. By integrating two‑dimensional phosphorene and bismuthene through interfacial engineering, the team successfully constructed a bifunctional electrode that combines high energy storage capacity with high sensing sensitivity, injecting new momentum into research in this field.
The study innovatively built a phosphorene/bismuthene (BP/Bi) 2D heterojunction synergistic system, achieving three major breakthroughs. First, liquid nitrogen‑assisted liquid‑phase exfoliation efficiently produced few‑layer phosphorene and bismuthene; the formation of P-O-Bi covalent interfacial bonds effectively suppressed the restacking of phosphorene nanosheets, greatly improving structural stability and electron transfer efficiency. Second, breakthrough electrochemical performance was achieved - the optimized BP/Bi (3:1) electrode delivered a high areal capacitance of 7.6 mF cm -2 and maintained 92.1% capacitance retention after 30,000 cycles, far superior to most reported micro‑supercapacitors. Third, by introducing DMSO into the gel electrolyte, the device retained 70% of its room‑temperature capacitance at -35 °C, demonstrating excellent freeze tolerance, and achieved 96% capacitance retention under 90° bending, providing key support for wearable applications in extreme environments.
Black phosphorus, an emerging 2D semiconductor material, possesses a unique corrugated structure and excellent physicochemical properties, showing great potential in the field of supercapacitors. However, BP intrinsically suffers from low electrical conductivity (300 S m -1 ) and poor environmental stability, limiting its cycle life and rate performance. Bismuthene, a 2D semimetal, has extremely high conductivity (4.6 × 10 4 S cm -1 ) and good lyophilicity. The team found that constructing the BP/Bi heterojunction with P-O-Bi covalent bridging not only stabilizes the crystal structure of BP but also creates high‑speed electron transport channels at the interface, significantly promoting ion diffusion and charge transfer.
The team initially used pure black phosphorus as the micro‑supercapacitor electrode but found that its capacitance retention was only 84.5% after 10,000 cycles. To address this, they adopted liquid nitrogen‑assisted low‑temperature liquid‑phase exfoliation combined with mask‑assisted vacuum filtration to prepare BP/Bi composites with different mass ratios (5:1, 3:1, 1:1, 1:3). Systematic electrochemical testing and structural characterization revealed that the 3:1 mass ratio gave the best performance: an areal capacitance of 7.46 mF cm -2 , excellent rate capability, 92.1% capacitance retention after 30,000 cycles, and a Coulombic efficiency of 91.5%. Moreover, the team monolithically integrated the BP/Bi micro‑supercapacitor with a pressure sensor on a flexible substrate using graphene as the flexible current collector, achieving highly sensitive monitoring of finger, wrist, and elbow bending movements with a fast response time of 48 ms and negligible signal attenuation over 1,500 cycles.
The interface‑stabilized phosphorene/bismuthene heterojunction micro‑supercapacitor developed by the research team combines ultra‑long cycle life, excellent freeze tolerance, and mechanical flexibility, while achieving seamless integration of energy storage and sensing. This makes the BP/Bi heterojunction composite a highly promising core component for next‑generation flexible wearable electronic systems, offering a brand‑new materials design paradigm for health monitoring, human‑machine interaction, and exploration in extreme environments.
DOI Link:
https://doi.org/10.26599/NR.2026.94908756
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Nano Research
Black Phosphorus/Bismuth Heterojunction Enables Freeze-Tolerant Micro-Supercapacitors and Integrated Sensing
20-Jul-2026