Sandra Hansen

Batteries play a critical role in achieving zero-emission goals and in the transition toward a more circular economy. Ensuring battery safety is a top priority for manufacturers and consumers alike, and hence is an active topic of research. Metal-oxide nanostructures have unique properties that make them highly promising for gas sensing in battery safety applications. In this study, we investigate the gas-sensing capabilities of semiconducting metal oxides for detecting vapors produced by common battery components, such as solvents, salts, or their degassing products. Our main objective is to develop sensors capable of early detection of common vapors produced by malfunctioning batteries to prevent explosions and further safety hazards. Typical electrolyte components and degassing products for the Li-ion, Li-S, or solid-state batteries that were investigated in this study include 1,3-dioxololane (C₃H₆O₂─DOL), 1,2-dimethoxyethane (C₄H₁₀O₂─DME), ethylene carbonate (C₃H₄O₃─EC), dimethyl carbonate (C₄H₁₀O₂─DMC), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO₃) salts in a mixture of DOL and DME, lithium hexafluorophosphate (LiPF₆), nitrogen dioxide (NO₂), and phosphorous pentafluoride (PF₅). Our sensing platform was based on ternary and binary heterostructures consisting of TiO₂(111)/CuO(1̅11)/Cu₂O(111) and CuO(1̅11)/Cu₂O(111), respectively, with various CuO layer thicknesses (10, 30, and 50 nm). We have analyzed these structures using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), micro-Raman spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy. We found that the sensors reliably detected DME C₄H₁₀O₂ vapors up to a concentration of 1000 ppm with a gas response of 136%, and concentrations as low as 1, 5, and 10 ppm with response values of approximately 7, 23, and 30%, respectively. Our devices can serve as 2-in-1 sensors, functioning as a temperature sensor at low operating temperatures and as a gas sensor at temperatures above 200 °C. Density functional theory calculations were also employed to study the adsorption of the vapors produced by battery solvents or their degassing products, as well as water, to investigate the impact of humidity. PF₅ and C₄H₁₀O₂ showed the most exothermic molecular interactions, which are consistent with our gas response investigations. Our results indicate that humidity does not impact the performance of the sensors, which is crucial for the early detection of thermal runaway under harsh conditions in Li-ion batteries. We show that our semiconducting metal-oxide sensors can detect the vapors produced by battery solvents and degassing products with high accuracy and can serve as high-performance battery safety sensors to prevent explosions in malfunctioning Li-ion batteries. Despite the fact that the sensors work independently of the type of battery, the work presented here is of particular interest for the monitoring of solid-state batteries, since DOL is a solvent typically used in this type of batteries.

Lithium-ion batteries are one of the most important energy storage devices of the future and pave the way for a greener society. In this context, the demand for batteries with high energy density is increasing significantly and is reaching the limits of the technology currently in use. Therefore, intensive research is being conducted to utilize a new class of materials for energy storage. The most promising alternatives to today's nickel-based cathode and graphite anode materials are silicon and sulfur. Both silicon and sulfur are abundant and cheap and possess extremely high theoretical specific capacities of 4200 mAh/g_Si and 1675 mAh/g_S, respectively. One of the biggest challenges with sulfur-based batteries is the polysulfide shuttle effect, which occurs with sulfur cathodes, leading to an insulating passivation layer, especially on the commonly used lithium metal anodes. Therefore, to replace lithium metal anodes with silicon, it is of major importance to understand the reactivity of polysulfides with silicon. To investigate the effect of lithium polysulfides on the performance of the anodes in the critical formation cycles, mesoporous silicon anodes were galvanostatically cycled in electrolytes containing different concentrations of polysulfides. In this process, the anodes were analyzed after one, five and ten cycles by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy to determine the composition of the SEI. Higher concentrations of polysulfides in the electrolyte result in more inorganic, oxide-containing species in the SEI. Silicon anodes with lower amounts of surface oxide show little or negative effect on the performance in the presence of polysulfides, while anodes with large amounts of surface oxide show higher impedance during cycling, an effect that is enhanced with increasing polysulfide content.

The initial formation cycles are critical to the performance of a lithium-ion battery (LIB), particularly in the case of silicon anodes, where the high surface area and extreme volume expansion during cycling make silicon susceptible to detrimental side reactions with the electrolyte. The solid electrolyte interface (SEI) that is formed during these initial cycles serves to protect the surface of the anode from a continued reaction with the electrolyte, and its composition reflects the composition of the electrolyte. In this work, ReaxFF reactive force field simulations were used to investigate the interactions between ether-based electrolytes with high LiTFSI salt concentrations (up to 4 mol/L) and a silicon oxide surface. The simulation investigations were verified with galvanostatic testing and post-mortem X-ray photoelectron spectroscopy, revealing that highly concentrated electrolytes resulted in the faster formation and SEIs containing more inorganic and silicon species. This study emphasizes the importance of understanding the link between electrolyte composition and SEI formation. This ReaxFF approach demonstrates an accessible way to tune electrolyte compositions for optimized performance without costly, time-consuming experimentation.

Fast detection of hydrogen gas leakage or its release in different environments, especially in large electric vehicle batteries, is a major challenge for sensing applications. In this study, the morphological, structural, chemical, optical, and electronic characterizations of ZnO:Eu nanowire arrays are reported and discussed in detail. In particular, the influence of different Eu concentrations during electrochemical deposition was investigated together with the sensing properties and mechanism. Surprisingly, by using only 10 μM Eu ions during deposition, the value of the gas response increased by a factor of nearly 130 compared to an undoped ZnO nanowire and we found an H₂ gas response of ∼7860 for a single ZnO:Eu nanowire device. Further, the synthesized nanowire sensors were tested with ultraviolet (UV) light and a range of test gases, showing a UV responsiveness of ∼12.8 and a good selectivity to 100 ppm H₂ gas. A dual-mode nanosensor is shown to detect UV/H₂ gas simultaneously for selective detection of H₂ during UV irradiation and its effect on the sensing mechanism. The nanowire sensing approach here demonstrates the feasibility of using such small devices to detect hydrogen leaks in harsh, small-scale environments, for example, stacked battery packs in mobile applications. In addition, the results obtained are supported through density functional theory-based simulations, which highlight the importance of rare earth nanoparticles on the oxide surface for improved sensitivity and selectivity of gas sensors, even at room temperature, thereby allowing, for instance, lower power consumption and denser deployment.

Monitoring volatile organic compounds (VOCs) in harsh environments, especially for safety applications, is a growing field that requires specialized sensor structures. In this work, we demonstrate the sensing properties toward the most common VOCs of columnar Al₂O₃/ZnO heterolayer-based sensors. We have also developed an approach to tune the sensor selectivity by changing the thickness of the exposed amorphous Al₂O₃ layer from 5 to 18 nm. Columnar ZnO films are prepared by a chemical solution method, where the exposed surface is decorated with an Al₂O₃ nanolayer via thermal atomic layer deposition at 75 °C. We have investigated the structure and morphology as well as the vibrational, chemical, electronic, and sensor properties of the Al₂O₃/ZnO heterostructures. Transmission electron microscopy (TEM) studies show that the upper layers consist of amorphous Al₂O₃ films. The heterostructures showed selectivity to 2-propanol vapors only within the range of 12-15 nm thicknesses of Al₂O₃, with the highest response value of ∼2000% reported for a thickness of 15 nm at the optimal working temperature of 350 °C. Density functional theory (DFT) calculations of the Al₂O₃/ZnO(1010) interface and its interaction with 2-propanol (2-C₃H₇OH), n-butanol (n-C₄H₉OH), ethanol (C₂H₅OH), acetone (CH₃COCH₃), hydrogen (H₂), and ammonia (NH₃) show that the molecular affinity for the Al₂O₃/ZnO(1010) interface decreases from 2-propanol (2-C₃H₇OH) ≈ n-butanol (n-C₄H₉OH) > ethanol (C₂H₅OH) > acetone (CH₃COCH₃) > hydrogen (H₂), which is consistent with our gas response experiments for the VOCs. Charge transfers between the surface and the adsorbates, and local densities of states of the interacting atoms, support the calculated strength of the molecular preferences. Our findings are highly important for the development of 2-propanol sensors and to our understanding of the effect of the heterojunction and the thickness of the top nanolayer on the gas response, which thus far have not been reported in the literature.

In this work, the gas sensing properties of the non-planar heterostructures based on CuO thin films, grown by the direct ink writing and covered with an ultrathin Al2O3 layer, are presented as a function of the operating temperature. The obtained results demonstrates the excellent selectivity to volatile organic compounds (VOCs) vapors, namely n-butanol and 2-propanol in a operating temperature range of 200 – 350 ºC. The relatively low gas response was observed at room temperature, which is very important for low-power operation. The dynamic gas response showed an ultra-fast response time of 2 – 3 s. The obtained results demonstrates the excellent potential of nonplanar heterostructures based on metal oxides for use in high-performance environmental monitoring applications.

Lithium-ion batteries (LIBs) still need continuous safety monitoring based on their intrinsic properties, as well as due to the increase in their sizes and device requirements. The main causes of fires and explosions in LIBs are heat leakage and the presence of highly inflammable components. Therefore, it is necessary to improve the safety of the batteries by preventing the generation of these gases and/or their early detection with sensors. The improvement of such safety sensors requires new approaches in their manufacturing. There is a growing role for research of nanostructured sensor’s durability in the field of ionizing radiation that also can induce structural changes in the LIB’s component materials, thus contributing to the elucidation of fundamental physicochemical processes; catalytic reactions or inhibitions of the chemical reactions on which the work of the sensors is based. A current method widely used in various fields, Direct Ink Writing (DIW), has been used to manufacture heterostructures of Al₂O₃/CuO and CuO:Fe₂O₃, followed by an additional ALD and thermal annealing step. The detection properties of these 3D-DIW printed heterostructures showed responses to 1,3-dioxolan (DOL), 1,2-dimethoxyethane (DME) vapors, as well as to typically used LIB electrolytes containing LiTFSI and LiNO₃ salts in a mixture of DOL:DME, as well also to LiPF₆ salts in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) at operating temperatures of 200 °C–350 °C with relatively high responses. The combination of the possibility to detect electrolyte vapors used in LIBs and size control by the 3D-DIW printing method makes these heterostructures extremely attractive in controlling the safety of batteries.

TiO₂/Cu₂O/CuO multi-nanolayers highly sensitive toward volatile organic compounds (VOCs) and H₂ have been grown in various thicknesses by a cost-effective and reproducible combined spray–sputtering–annealing approach. The ultrathin TiO₂ films were deposited by spray pyrolysis on top of sputtered–annealed Cu₂O/CuO nanolayers to enhance their gas sensing performance and improve their protection against corrosion at high operating temperatures. The prepared heterostructures were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and ultraviolet visible (UV–vis) and micro-Raman spectroscopy. The gas sensing properties were measured at several operating temperatures, where the nanolayered sensors with oxide thicknesses between 20 and 30 nm (Cu₂O/CuO nanolayers) exhibited a high response and an excellent selectivity to ethanol vapor after thermal annealing the samples at 420 °C. The results obtained at an operating temperature of 350 °C demonstrate that the CuO/Cu₂O nanolayers with thicknesses between 20 and 30 nm are sensitive mainly to ethanol vapor, with a response of ∼150. The response changes from ethanol vapors to hydrogen gas as the thickness of the CuO/Cu₂O nanolayers changes from 50 to 20 nm. Density functional theory-based calculations were carried out for the geometries of the CuO(1̅11)/Cu₂O(111) and TiO₂(111)/CuO(1̅11)/Cu₂O(111) heterostructures and their sensing mechanism toward alcohols of different chain lengths and molecular hydrogen. The reconstructed hexagonal Cu₂O(111) surface and the reconstructed monoclinic CuO(1̅11) and TiO₂(111) facets, all of which terminate in an O layer, lead to the lowest surface energies for each isolated material. We studied the formation of the binary and ternary heteroepitaxial interfaces for the surface planes with the best-matching lattices. Despite the impact of the Cu₂O(111) substrate in lowering the atomic charges of the CuO(1̅11) adlayer in the binary sensor, we found that it is the different surface structures of the CuO(1̅11)/Cu₂O(111) and TiO₂(111)/CuO(1̅11)/Cu₂O(111) devices that are fundamental in driving the change in the sensitivity response observed experimentally. The experimental data, supported by the computational results, are important in understanding the use of the multi-nanolayered films tested in this work as reliable, accurate, and selective sensor structures for the tracking of gases at low concentrations.

Continuous improvements in battery technology has paved the way for adoption in growing number of applications. However, the state-of-the-art graphite anodes remain sensitive to heat dissipation during fast charging or short circuits, and possibly causing inflammation of the battery. This is a limitation for safety critical applications and prevents ultra-high charging rates. In addition, power electronics is required for preventing hazardous and inefficient operating conditions, maximizing, for example, the lifetime of the battery system. Batteries with silicon anodes overcome the limitations of today?s battery technology and enable charging rates of multiple Cs, while operating up to 100 °C and being non-flammable. Nevertheless, this does not reduce requirements for the battery management system (BMS) to control the performance of the battery. The BMS needs to maximize the charging rate, limit mechanical stress of the battery electrodes, which is associated to high charging rates. Thus, obtaining high charging efficiency, while equalizing useful remaining lifetime for all battery stacks. This manuscript is a conceptional review of how silicon anodes could be used in future Lithium-ion (Li-ion) or Li sulfur batteries providing high energy densities, offering the possibility to charge batteries with higher current densities and faster charging times. BMS and the required power electronic converters for integrating battery storage are introduced and their application for the next generation of ultra-fast charging battery system is presented.

A comparative investigation of the post-electroplating treatment influence on the gas detecting performances of single ZnO nanorod/nanowire (NR/NW), as grown by electrochemical deposition (ECD) and integrated into nanosensor devices, is presented. In this work, hydrothermal treatment (HT) in a H₂O steam and conventional thermal annealing (CTA) in a furnace at 150 °C in ambient were used as post-growth treatments to improve the material properties. Herein, the morphological, optical, chemical, structural, vibrational, and gas sensing performances of the as-electrodeposited and treated specimens are investigated and presented in detail. By varying the growth temperature and type of post-growth treatment, the morphology is maintained, whereas the optical and structural properties show increased sample crystallization. It is shown that HT in H₂O vapors affects the optical and vibrational properties of the material. After investigation of nanodevices based on single ZnO NR/NWs, it was observed that higher temperature during the synthesis results in a higher gas response to H₂ gas within the investigated operating temperature range from 25 to 150 °C. CTA and HT or autoclave treatment showed the capability of a further increase in gas response of the prepared sensors by a factor of ∼8. Density functional theory calculations reveal structural and electronic band changes in ZnO surfaces as a result of strong interaction with H₂ gas molecules. Our results demonstrate that high-performance devices can be obtained with high-crystallinity NWs/NRs after HT. The obtained devices could be the key element for flexible nanoelectronics and wearable electronics and have attracted great interest due to their unique specifications.