Lithium-ion batteries suffer severe power loss at temperatures below zero degrees Celsius, limiting their use in applications such as electric cars in cold climates and high-altitude drones. The practical consequences of such power loss are the need for larger, more expensive battery packs to perform engine cold cranking, slow charging in cold weather, restricted regenerative braking, and reduction of vehicle cruise range by as much as 40 per cent. Previous attempts to improve the low-temperature performance of lithium-ion batteries have focused on developing additives to improve the low-temperature behaviour of electrolytes, and on externally heating and insulating the cells. Here we report a lithium-ion battery structure, the 'all-climate battery' cell, that heats itself up from below zero degrees Celsius without requiring external heating devices or electrolyte additives. The self-heating mechanism creates an electrochemical interface that is favourable for high discharge/charge power. We show that the internal warm-up of such a cell to zero degrees Celsius occurs within 20 seconds at minus 20 degrees Celsius and within 30 seconds at minus 30 degrees Celsius, consuming only 3.8 per cent and 5.5 per cent of cell capacity, respectively. The self-heated all-climate battery cell yields a discharge/regeneration power of 1,061/1,425 watts per kilogram at a 50 per cent state of charge and at minus 30 degrees Celsius, delivering 6.4-12.3 times the power of state-of-the-art lithium-ion cells. We expect the all-climate battery to enable engine stop-start technology capable of saving 5-10 per cent of the fuel for 80 million new vehicles manufactured every year. Given that only a small fraction of the battery energy is used for self-heating, we envisage that the all-climate battery cell may also prove useful for plug-in electric vehicles, robotics and space exploration applications.
Substantially reduced energy and power capabilities of lithium-ion cell operating at low temperatures pose a technical barrier for market penetration of hybrid electric vehicles and pure electric vehicles. The present work delineates Li-ion cell behaviors at low temperatures by a combined experimental and modeling approach. An electrochemical-thermal coupled model, incorporating concentration-and temperature-dependent transport and kinetic properties, is applied and validated against 2.2Ah 18650 cylindrical cells over a wide range of temperatures (−20 • C to 45 • C) and discharge rates. Simulation and experimental results demonstrate the dramatic effects of cell self-heating upon electrochemical performance. A nonisothermal Ragone plot accounting for these important thermal effects is proposed for the first time for Li-ion cells and more generally for thermally coupled batteries. Detailed resistance analysis indicates that performance limits at −20 • C depend on not only discharge rates but also thermal conditions. Optimization of cell design parameters and material properties is performed for 1 C rate discharge starting from −20 • C, where the principal performance limitations are found to be Li + diffusion in the electrolyte and solid-state Li diffusion in graphite particles, instead of charge-transfer kinetic or ohmic resistance.
Abstract. Vanillin (VL), a phenolic aromatic carbonyl abundant in biomass burning emissions, forms triplet excited states (3VL∗) under simulated sunlight leading to aqueous secondary organic aerosol (aqSOA) formation. Nitrate and ammonium are among the main components of biomass burning aerosols and cloud or fog water. Under atmospherically relevant cloud and fog conditions, solutions composed of either VL only or VL with ammonium nitrate were subjected to simulated sunlight irradiation to compare aqSOA formation via the direct photosensitized oxidation of VL in the absence and presence of ammonium nitrate. The reactions were characterized by examining the VL decay kinetics, product compositions, and light absorbance changes. Both conditions generated oligomers, functionalized monomers, and oxygenated ring-opening products, and ammonium nitrate promoted functionalization and nitration, likely due to its photolysis products (⚫OH, ⚫NO2, and NO2- or HONO). Moreover, a potential imidazole derivative observed in the presence of ammonium nitrate suggested that ammonium participated in the reactions. The majority of the most abundant products from both conditions were potential brown carbon (BrC) chromophores. The effects of oxygen (O2), pH, and reactants concentration and molar ratios on the reactions were also explored. Our findings show that O2 plays an essential role in the reactions, and oligomer formation was enhanced at pH <4. Also, functionalization was dominant at low VL concentrations, whereas oligomerization was favored at high VL concentrations. Furthermore, oligomers and hydroxylated products were detected from the oxidation of guaiacol (a non-carbonyl phenol) via VL photosensitized reactions. Last, potential aqSOA formation pathways via the direct photosensitized oxidation of VL in the absence and presence of ammonium nitrate were proposed. This study indicates that the direct photosensitized oxidation of VL may be an important aqSOA source in areas influenced by biomass burning and underscores the importance of nitrate in the aqueous-phase processing of aromatic carbonyls.
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