Operando monitoring of complex physical and chemical activities inside rechargeable lithium-ion batteries during thermal runaway is critical to understanding thermal runaway mechanisms and giving early warning of safety-related failure. However, most existing sensors cannot survive during such extremely hazardous thermal runaway processes (temperature up to 500 °C accompanied by fire and explosion). To address this, we develop a compact and multifunctional optical fiber sensor (12 mm in length and 125 µm in diameter) capable of insertion into commercial 18650 cells to continuously monitor internal temperature and pressure effects during cell thermal runaway. We observe a stable and reproducible correlation between the cell thermal runaway and the optical response. The sensor’s signal shows two internal pressure peaks corresponding to safety venting and initiation of thermal runaway. Further analysis reveals that a scalable solution for predicting imminent thermal runaway is the detection of the abrupt turning range of the differential curves of cell temperature and pressure, which corresponds to an internal transformation between the cell reversible and irreversible reactions. By raising an alert even before safety venting, this new operando measurement tool can provide crucial capabilities in cell safety assessment and warning of thermal runaway.
Surface plasmon polaritons (SPP) can be excited on metal-coated optical fibres, enabling the accurate monitoring of refractive index changes. Configurations reported so far mainly operate in liquids but not in air because of a mismatch between permittivities of guided light modes and the surrounding medium. Here we demonstrate a plasmonic optical fibre platform that overcomes this limitation. The underpinning of our work is a grating architecture—a gold-coated highly tilted Bragg grating—that excites a spectral comb of narrowband-cladding modes with effective indices near 1.0 and below. Using conventional spectral interrogation, we measure shifts of the SPP-matched resonances in response to static atmospheric pressure changes. A dynamic experiment conducted using a laser lined-up with an SPP-matched resonance demonstrates the ability to detect an acoustic wave with a resolution of 10−8 refractive index unit (RIU). We believe that this configuration opens research directions for highly sensitive plasmonic sensing in gas.
In situ and continuous monitoring of electrochemical activity is key to understanding and evaluating the operation mechanism and efficiency of energy storage devices. However, this task remains challenging. For example, the present methods are not capable of providing the real-time information about the state of charge (SOC) of the energy storage devices while in operation. To address this, a novel approach based on an electrochemical surface plasmon resonance (SPR) optical fiber sensor is proposed here. This approach offers the capability of in situ comprehensive monitoring of the electrochemical activity (the electrode potential and the SOC) of supercapacitors (used as an example). The sensor adopted is a tilted fiber Bragg grating imprinted in a commercial single-mode fiber and coated with a nanoscale gold film for high-efficiency SPR excitation. Unlike conventional “bulk” detection methods for electrode activity, our approach targets the “localized” (sub-μm-scale) charge state of the ions adjacent to the electrode interface of supercapacitors by monitoring the properties of the SPR wave on the fiber sensor surface located adjacent to the electrode. A stable and reproducible correlation between the real-time charge–discharge cycles of the supercapacitors and the optical transmission of the optical fiber has been found. Moreover, the method proposed is inherently immune to temperature cross-talk because of the presence of environmentally insensitive reference features in the optical transmission spectrum of the devices. Finally, this particular application is ideally suited to the fundamental qualities of optical fiber sensors, such as their compact size, flexible shape, and remote operation capability, thereby opening the way for other opportunities for electrochemical monitoring in various hard-to-reach spaces and remote environments.
Understanding ion transport kinetics and electrolyte-electrode interactions at electrode surfaces of batteries in operation is essential to determine their performance and state of health. However, it remains a challenging task to capture in real time the details of surface-localized and rapid ion transport at the microscale. To address this, a promising approach based on an optical fiber plasmonic sensor capable of being inserted near the electrode surface of a working battery to monitor its electrochemical kinetics without disturbing its operation is demonstrated using aqueous Zn-ion batteries as an example. The miniature and chemically inert sensor detects perturbations of surface plasmon waves propagating on its surface to rapidly screen localized electrochemical events on a sub-μm-scale thickness adjacent to the electrode interface. A stable and reproducible correlation between the real-time ion insertions over charge-discharge cycles and the optical plasmon response has been observed and quantified. This new operando measurement tool will provide crucial additional capabilities to battery monitoring methods and help guide the design of better batteries with improved electro-chemistries.
The apparent increase in hormone-induced cancers and disorders of the reproductive tract has led to a growing demand for new technologies capable of detecting endocrine disruptors. However, a long-lasting challenge unaddressed is how to achieve ultrahigh sensitive, continuous, and in situ measurement with a portable device for in-field and remote environmental monitoring. Here we demonstrate a simple-to-implement plasmonic optical fiber biosensing platform to achieve an improved light–matter interaction and advanced surface chemistry for ultrasensitive detection of endocrine disruptors. Our platform is based on a gold-coated highly tilted fiber Bragg grating that excites high-density narrow cladding mode spectral combs that overlap with the broad absorption of the surface plasmon for high accuracy interrogation, hence enabling the ultrasensitive monitoring of refractive index changes at the fiber surface. Through the use of estrogen receptors as the model, we design an estradiol–streptavidin conjugate with the assistance of molecular dynamics, converting the specific recognition of environmental estrogens (EEs) by estrogen receptor into surface-based affinity bioassay for protein. The ultrasensitive platform with conjugate-induced amplification biosensing approach enables the subsequent detection for EEs down to 1.5 × 10−3 ng ml−1 estradiol equivalent concentration level, which is one order lower than the defined maximal E2 level in drinking water set by the Japanese government. The capability to detect EEs down to nanogram per liter level is the lowest limit of detection for any estrogen receptor-based detection reported thus far. Its compact size, flexible shape, and remote operation capability open the way for detecting other endocrine disruptors with ultrahigh sensitivity and in various hard-to-reach spaces, thereby having the potential to revolutionize environment and health monitoring.
Operando tracking the chemical dynamics/states of a battery and its components is critical to their second life for boosting their sustainability. Herein, we demonstrate the feasibility and diversity of the tilted fiber Bragg grating (TFBG) optical fiber sensors to operando access the chemistry and states of electrolytes. We show how a single TFBG sensor can simultaneously measure the temperature and refractive index evolution inside the batteries, which pertains to the chemical evolution of the electrolyte. We also, for the first time, monitor the turbidity of electrolytes via the particulate-induced optical scattering and absorption. These unravelled electrolyte characteristics by TFBG help determine the electrochemical reaction pathways, being strongly correlated to the capacity loss. This type of sensing offers intriguing opportunities to building a “lab-on-fiber” platform for deeper chemistry and practical applications, provided we can delicately converge electrochemistry, photonics, and data science.