Key Takeaways & Executive Findings
- •• • The optimized BP/Bi (3:1) heterojunction electrode delivers an areal capacitance of 7.6 mF·cm−2, a 1.6-fold enhancement over pure BP, directly addressing the low energy density bottleneck in BP-based micro-supercapacitors. • • The device retains 92.1% of its initial capacitance after 30,000 charge/discharge cycles, demonstrating exceptional long-term operational stability critical for reliable wearable electronics. • • With DMSO-modified gel electrolyte, the MSC maintains 70% of room-temperature capacitance at −35 °C, enabling freeze-tolerant operation for extreme-environment applications. • • The integrated system exhibits ultra-fast response time of ~48 ms and negligible signal attenuation over 900 cycles, validating its suitability for real-time physiological monitoring.
Abstract
Black phosphorus (BP)-based micro-supercapacitors (MSCs) are promising for wearable electronics but suffer from intrinsic instability and sluggish electron kinetics. Here, we report a two-dimensional phosphorene/bismuthene (2D BP/Bi) heterojunction fabricated via liquid nitrogen-assisted exfoliation and mask-assisted filtration, serving as a robust bifunctional electrode for integrated flexible energy-sensing systems. The heterostructure suppresses nanosheet restacking and enhances interfacial stability through strong P–O–Bi covalent bonding and interfacial synergy. Bismuthene incorporation constructs high-speed electron transport channels, facilitating ion diffusion and charge transfer. The optimized BP/Bi (3:1) electrode achieves a high areal capacitance of 7.6 mF·cm−2 (1.6-fold enhancement over pure BP) and ultra-long lifespan with 92.1% retention after 30,000 cycles. By tailoring the gel electrolyte with DMSO, the device exhibits remarkable freeze-tolerance, maintaining 70% capacitance at −35 °C. An all-flexible integrated system combining the MSC with a pressure sensor using graphene current collectors enables continuous, self-sustained physiological monitoring. This work offers critical insights into interface engineering for high-performance BP-based MSCs and paves the way for extreme-environment wearable applications.
1. Introduction
Conventional wearable systems rely on discrete power sources, sensors, and connectors, resulting in bulky configurations, poor mechanical conformability, and performance degradation under dynamic deformation. These limitations hinder their integration into complex human-centric scenarios, such as real-time health monitoring and human-machine interaction. Planar micro-supercapacitors (MSCs) offer a promising solution due to their mechanical flexibility, safety, and potential for miniaturization and system integration. However, the performance of BP-based MSCs is hampered by BP's intrinsic instability and low electrical conductivity, leading to rapid capacity decay and poor rate capability.
This work addresses these bottlenecks by constructing a 2D BP/Bi heterojunction via liquid nitrogen-assisted exfoliation and mask-assisted filtration. The strong P–O–Bi covalent bonding at the interface not only suppresses nanosheet restacking but also enhances interfacial stability, while bismuthene provides high-speed electron transport channels. This synergistic design significantly improves ion diffusion and charge transfer, resulting in high areal capacitance, ultra-long cycling stability, and freeze-tolerance. The integration of such MSCs with pressure sensors on graphene current collectors demonstrates a monolithic flexible system capable of continuous physiological monitoring, offering a generalizable paradigm for next-generation wearable electronics.
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Yukai Chang, Chenfang Lou, Jin Jia, Huilan Zhao, Penghui Li, Yingjie Huo, Libo Wang, Qianku Hu, Yuanyuan Zhu, Aiguo Zhou (2026). Interface-stabilized phosphorene/bismuthene heterostructures for freeze-tolerant micro-supercapacitors and integrated sensing. SinoTechIntel Verified Research. https://doi.org/10.26599/NR.2026.94908756
Research & Educational Purpose Only:The translations, structured abstracts, analytical annotations, and data reports provided by SinoTechIntel are intended exclusively for academic research, internal corporate R&D, and educational benchmarking. They do not constitute formal engineering, chemical safety, legal, or professional advice.
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Frequently Asked Questions
What is the specific role of P–O–Bi covalent bonding in enhancing the electrochemical stability of the BP/Bi heterostructure?
The P–O–Bi covalent bonds anchor bismuthene onto phosphorene, preventing restacking and passivating reactive phosphorus sites. This suppresses degradation and maintains structural integrity, contributing to the 92.1% capacitance retention after 30,000 cycles.
How does the DMSO-modified gel electrolyte enable freeze-tolerance down to -35 °C?
DMSO acts as a cryoprotectant, lowering the freezing point of the aqueous electrolyte and maintaining ionic conductivity at sub-zero temperatures. This allows the device to retain 70% of its room-temperature capacitance at -35 °C.
The methods are solution-based and potentially scalable, but achieving uniform heterojunction formation and precise electrode patterning at large scales remains challenging. The reported areal capacitance of 7.6 mF·cm−2 suggests feasibility for micro-devices, but roll-to-roll processing would require further optimization.
How does the integrated system maintain signal integrity during repeated mechanical deformation?
The use of graphene as a flexible current collector and the robust interfacial bonding within the electrode ensure mechanical conformability. The system shows negligible signal attenuation over 900 cycles, indicating stable electrical contact and structural resilience under bending.
What is the cost comparison of BP/Bi heterostructures versus conventional electrode materials for MSCs?
Bismuth is relatively inexpensive, but black phosphorus production is costly and requires careful handling. The enhanced performance and longevity may offset initial costs, but a detailed techno-economic analysis is not provided in the paper.
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