Batteries based on alternatives to lithium are now of global research interest. Magnesium metal batteries are particularly attractive for their potential high energy density. Polymer electrolytes for high density rechargeable batteries have been sought for decades, due to their improved thermal stability compared with liquids and their lower density and cost compared with inorganic solids. Yet, little success has so far been realized in polymer electrolytes for magnesium metal batteries. In this review, the magnesium polymer electrolyte literature is comprehensively explored. Differences between requirements for lithium polymer and magnesium polymer batteries are discussed as well as the consequences on necessary considerations for impactful magnesium polymer electrolyte research.
In this work, we develop a label-free electrochemical immunosensor for the detection of interleukin-6 (IL-6) in human cerebrospinal fluid (CSF) and serum for diagnostic and therapeutic monitoring. The IL-6 immunosensor is fabricated from gold interdigitated electrode arrays (IDEAs) that are modified with IL-6 antibodies for direct antigen recognition and capture. A rigorous surface analysis of the sensor architecture was conducted to ensure high structural fidelity and performance. Electrochemical characterization was conducted by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and sensing was performed using differential pulse voltammetry (DPV). The DPV peak current was used to quantify IL-6 in buffer, CSF, and serum in the range 1 pg mL–1 < [IL-6] < 1 μg mL–1. The IL-6 IDEA sensor achieved a limit of detection (LOD) of 1.63 pg mL–1 in PBS, 2.34 pg mL–1 in human CSF, and 11.83 pg mL–1 in human serum. The sensor response is linear in the concentration range 10 pg mL–1 < [IL-6] < 10 ng mL–1, and the sensor is selective for IL-6 over other common cytokines, including IL-10 and TNF-α. EIS measurements showed that the resistance to charge transfer, RCT, decreases upon IL-6 binding, an observation attributed to a structural change upon Ab-Ag binding that opens up the architecture so that the redox probe can more easily access the electrode surface. The IL-6 IDEA sensor can be used as a point-of-care diagnostic tool to deliver rapid results (∼3 min) in clinical settings for traumatic brain injury, and potentially address the unmet need for effective diagnostic and prognostic tools for other cytokine-related illnesses, such as sepsis and COVID-19 induced cytokine storms. Given the interdigitated electrode form factor, it is likely that the performance of the sensor can be further improved through redox cycling.
Solid-state single-ion conducting polymer electrolytes have drawn considerable interest for secondary lithium batteries due to their potential for high electrochemical stability and safety, but applications are limited by their low ionic conductivities. Specifically, poly(ethylene oxide) (PEO) based electrolytes have the highest reported Li+ conductivities for these materials; however, their potential is limited due to the ion transport mechanism being coupled to segmental relaxations of the cation solvating polymer chain. To investigate the potential of single-ion conducting polymer electrolytes lacking polar matrices, we synthesized three para-polyphenylene-based, side-chain polymer electrolytes with various pendent anion chemistries (–SO3−, –PSI−, and –TFSI−) with differing binding affinities to Li+. Compared with the previously reported lithium poly(4-styrenesulfonyl(trifluoromethylsulfonyl)imide) (LiPSTFSI), the side-chain polymers showed at least 3 orders of magnitude higher conductivity with the same –TFSI− anion (6.7 × 10−6 S cm−1 compared with 1.2 × 10−10 S cm−1 at 150 °C). We found that the side-chain electrolyte showed a dielectric relaxation dominated transport mechanism through use of dielectric spectroscopy analysis. The conductivity is highly dependent on the charge delocalization and size of the pendent anion, which provides a pathway forward for the engineering of polymeric ion conductors for electrochemical applications.
Magnesium-ion-conducting solid polymer electrolytes have been studied for rechargeable Mg metal batteries, one of the beyond-Li-ion systems. In this paper, magnesium polymer electrolytes with magnesium bis(trifluoromethane)sulfonimide (Mg(TFSI) 2 ) salt in poly( ε -caprolactone- co -trimethylene carbonate) (PCL-PTMC) were investigated and compared with the poly(ethylene oxide) (PEO) analogs. Both thermal properties and vibrational spectroscopy indicated that the total ion conduction in the PEO electrolytes was dominated by the anion conduction due to strong polymer coordination with fully dissociated Mg 2+ . On the other hand, in PCL-PTMC electrolytes, there is relatively weaker polymer–cation coordination and increased anion–cation coordination. Sporadic Mg- and F-rich particles were observed on the Cu electrodes after polarization tests in Cu|Mg cells with PCL-PTMC electrolyte, suggesting that Mg was conducted in the ion complex form (Mg x TFSI y ) to the copper working electrode to be reduced which resulted in anion decomposition. However, the Mg metal deposition/stripping was not favorable with either Mg(TFSI) 2 in PCL-PTMC or Mg(TFSI) 2 in PEO, which inhibited quantitative analysis of magnesium conduction. A remaining challenge is thus to accurately assess transport numbers in these systems.